Phase Transitions and Crystal Symmetry (PDFDrive)

Phase Transitions and Crystal Symmetry
Fundamental Theories of Physics
An International Book Series on The Fundamental Theories of Physics:

Their Clarification, Development and Application
Editor: ALWYN V AN DER MERWE

University of Denver, U.SA.
Editorial Advisory Board:

ASIM BARUT, University of Colorado, U.SA.
HERMANN BONDI, University of Cambridge, UK.
BRIAN D. JOSEPHSON, University of Cambridge, UK.
CLIVE KILMISTER, University of London, UK.
GUNTER LUDWIG, Philipps-Universitat, Marburg, F R.G.
NATHAN ROSEN, Israel Institute of Technology, Israel
MENDEL SACHS, State University of New York at Buffalo, U.SA.
ABDUS SALAM, International Centre for Theoretical Physics, Trieste, Italy
HANS-JORGEN TREDER, Zentralinstitutfur Astrophysik der Akademie der
Wissensc haften , GDR.
Volume 38
Phase Transitions and
Crystal Symmetry
by
Yu. A. IZYUMOV
and
V. N. SYROMYATNIKOV
Institute of Metal Physics,
Ural Division of the U.S.S.R. Academy of Sciences,
Sverdlovsk, U.S.S.R .
..
KLUWER ACADEMIC PUBLISHERS
DORDRECHT I BOSTON I LONDON
Library of Congress Cataloging in Publication Data
Izlumov, f'U. A. (f'Uri) Aleksandrovich), 1933-
[Fazovye perekhody i simmetriJa kristallov. English]
Phase transitions and crystal symmetry I by Yu.A. Izyumov and V.N.
Syromyatnikov.
p. cm. -- (Fundamental theories of physics)
Rev. and enl. translation of: Fazovye perekhody i simmetriJa
kristallov.
Includes bibliographlcal references.
1. Crystallography. 2. Phase transformations (Statistical
physiCS) 3. Symmetry (Physics) I. SyromJatnikov, V. N. (Vladimir
N';i<.o1aavlch) II. Izlumov. ro. A. (IUri1 Aleksandrovich), 1933-
Fazovye perekhody i simmetriJa kristallov. III. Title. IV. Series.
QD921.19413 1990
548' .5--dc20 89-71632
CIP
ISBN-13: 978-94-010-7357-8 e-ISBN-13: 978-94-009-1920-4
DOl: 10.1007/978-94-009-1920-4
Published by Kluwer Academic Publishers,

P,O. Box 17, 3300 AA Dordrecht, The Netherlands.
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Printed on acid-free paper
This is the expanded and revised translation of the original work

$A30BhIE TIEPEXO.llhI I1 CI1MMETPIUI KPI1CTAJIJIOB
Published by Nauka Publishers, Moscow, © 1984.
Translated from the Russian by A.P. Zavarnitsyn
All Rights Reserved

This English edition © 1990 by Kluwer Academic Publishers
Softcover reprint of the hardcover 1st edition 1990
No part of the material protected by this copyright notice may be reproduced or

utilized in any form or by any means, electronic or mechanical,
including photocopying, recording or by any information storage and
retrieval system, without written permiGsion from the copyright owner.
Contents
Preface . . . . . . . . . . . . Xlll
Preface to the English Edition XVll
Notation . . . . . . . . . . . XIX
Chapter 1. Introduction to Phenomenological Phase Transition

Theory . . . . . . . . . . . . . . . . . . . . . . 1
1. Fundamentals of Landau's Thermodynamic Theory 1
Elementary thermodynamic analysis (1). Spontaneous symmetry
breaking at a continuous phase transition (7). The Landau condi-
tion for a second-order phase transition (9). Further development of
Landau's theory (10).
2. Prerequisites on Space-group Representations . . . . . . . . . . . 12
Space-group irreducible representations (12). Irreducible representa-
tions and their decomposition (15).
References . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Chapter 2. Physical Realization of the Order Parameters at a Micro-

scopic Level of Description . . . . . . . . . . . . . 19
3. Tensor Representation of the Space Group on a Basis of Localized
Atomic Functions 19
Constructing crystal space group reducible representations (20). The
stabilizer method (24). Constructing basis functions for star arms
(27).
4. Permutational Representation and its Basis . . . . . . . . . . . . 28
A summary of formulas (28). The OP for ordering in AB type alloys
(29). The OP for ordering in Nb-H and Ta-H hydrides (30).
VI CONTENTS
5. Vector Representation and its Basis . . . . . . . . . . . . . . . 36

A summary offormulas (36). The OP at a structural phase transition
in A-15 compounds (38). The OP at a structural phase transition in
C-15 compounds (43).
6. Pseudovector Representation and its Basis . . . . . . . . . . . . 45
A description of the magnetically ordered state (45). The OP at a
magnetic phase transition in a garnet (47).
References 51
Chapter 3. Symmetry Change at Phase Transitions 52

7. Change in Translational Symmetry. . . . . . . . . 52
The Brillouin zone and the symmetric points in it (52). Arm mixing
and the transition channel (56). Magnetic lattices (72).
8. The Total Symmetry Change . . . . . . . . . . . . . . . . . . 74
Principles for finding the symmetry group of a new phase (74). An
example of a group-theoretic method of searching for dissymmetric
phases (77).
9. Domains . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
Domains as a consequence of the Curie principle (82). A symme-
try classification of domains (83). Arm, orientational and antiphase
domains (85). Examples of an analysis of the domain structure (87).
10. The Paraphase . . . . . . . . . . . . . . . . . . . . . . . . 91
The initial phase and the paraphase (91). Major criteria for para-
phase search (93). An example of choosing the paraphase (94).
References . . . . . . . . . . . . . . . . . . . . . . . 98
Chapter 4. Analysis of the Thermodynamic Potential 100

11. Invariant Expressions of the Thermodynamic Potential . 100
A straightforward (direct) method of constructing polynomial invari-
ants (100). Constructing the for the structural phase transition in
C-15 compounds (101). Constructing the for the structural phase
transition in A-15 compounds (102).
12. Integral Rational Basis of Invariants . . . . . . . . . . . . . . 104
General remarks (104). The IRBI construction algorithm (105). Solv-
ability of the group and the minimal IRBI (110).
13. Examples of the Construction of an IRBI . . . . . . . . . . . . 112
Constructing the IRBI for the structural transition in C-15 com-
pounds (112). Construction of the IRBI for the structural transition
CONTENTS VB
in A-15 compounds (114). Constructing the IRBI for the structural

transition in MnAs (117).
14. Irreducible Representation Images and Thermodynamic Potential
Types 118
General information on the I groups (118). Two- and three-compon-
ent order parameters (119). A multicomponent order parameter (121).
I groups and rotation groups in multidimensional space (121). Uni-
versal classes (123).
References . . . . . . . . . . . . . . . . . . . . . . . . . . 130
Chapter 5. Phase Diagrams in the Space of Thermodynamic

Potential Parameters . . . . . . . . . . . . 131
15. Theoretical Fundamentals of the Phase Diagram Construction
Method 131
Major physical principles (131). Requisite theorems from the algebra
of polynomials (134).
16. The One-Component Order Parameter . . . . . . . . . . . . . 137
The form ofthe thermodynamic potential (137). The 17 6 model (137).
The 1]8 model (139). Succession of solutions to equations of state
(146).
17. The Two-Component Order Parameter . . . . . . . . . . . . . 148
The 1]4 model (148). The 1]6 model (152). Cubic invariants in the 7,4
model (156). Cubic invariants in the 1]6 model (159).

18. The Three-Component Order Parameter . . . . . . . . . . . . 161
The phases and the stability conditions (161). The phase diagram in
the 17 4 model (164).
19. The Role of the IRBI in the Construction of Phase Diagrams . . . 165
The two-component order parameter (166). The three-component
order parameter (167).
20. Coupling Order Parameters . . . . . . . . . . . . . . . . . . 168
The interplay of two one-component order parameters (168). Phase
transitions in MnAs (170). Phase transitions in KMnF 3 (173). Ori-
entation transitions (178).
References . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
Vill CONTENTS
Chapter 6. Macroscopic Order Parameters 188

21. Transformation Properties of the Order Parameters 188
Physical realization of the macroparameters (188). Construction of
basis functions (191). Constructing the thermodynamic potential
(192).
22. Interplay of Micro- and Macroparameters . . . . . . . . . . . . 197
Constructing the thermodynamic potential (197). Improper transi-
tions (198). Examples of structural transitions in perovskite-type
crystals (199).
23. Ferroics 202
Classification of dissymmetric phases according to macroproperties
(202). Ferroelectrics (204). Ferroelastics (205). Ferrobielectrics and
ferrobimagnetics (205). Higher-order ferroics (206).
24. Non-ferroics . . . . . . . . . . . . . . . . . 211
Crystal-class-preserving phase transitions (211). Examples of non-
ferroics (212).
References . . . . . . . . . . . . . . . . . . . 214
Chapter 7. Phase Transitions in an External Field 215

25. Phase Diagrams . . . . . . . . . . . . . . . . . 215
Constructing a potential for a system in an external field (215).
Phase diagram for the 1]4 model (216). Phase diagram for the 1]6
model (217). Singular points on the phase diagram (222). Multi-
component order parameter (222). Splitting of a phase transition
described by a microparameter in an external field (226).
26. Features Peculiar to the Temperature Behavior of Susceptibility in
the Vicinity of the Second-Order Phase Transition . . . . . " 227
Classification of the singularities by the Aizu indices (227). Catas-
trophe indices (231).
27. Calculation of Susceptibilities for Second-Order Phase Transitions . 233
Proper phase transitions (233). Improper phase transitions (234).
Pseudoproper phase transitions (238).
28. Singularities of the Susceptibility in the Vicinity of the First-Order
Phase Transition 239
Classification of the first-order transitions (239). Classifying the sin-
gularities of susceptibilities (240). Calculating the susceptibilities
(243).
CONTENTS IX
29. Domains in an External Field . . . . . . . . . . . . . . . . . 244

A thermodynamic description of the domains (244). Effect of an
external field on domains (247).
References . . . . . . . . . . . . . . . 249
Chapter 8. Martensite Transformations 250

30. Reconstructive Structural Transitions 250
Transitions without group-subgroup relation (250). Geometric rela-
tion of direct lattices (253). The b.c.c.-f.c.c. transition (255). The
b.c.c.-h.c.p. transition (256). The f.c.c.-h.c.p. transition (257). Ori-
entation relations (258). Interrelationship ofreciprocallattices (261).
31. Thermodynamic Analysis of the Homogeneous State . . . . . . . 266
Describing the martensitic transition in terms of deformation (266).
Thermodynamic potential and phase diagram (268). Behavior in an
external field (270). Shape memory effect (274).
32. Inhomogeneous States in the Vicinity of the Phase Transition . . . 275
Thermodynamic potential with gradient terms (275). Equations of
motion (277). Tetragonal-strain phase transition (278). Phase tran-
sition with shear strain (282). Square lattice (288).
33. The Omega Phase . . . . . . . . . . . . . . . . . . . . . . 292
Interrelationship between the lattices at the b.c.c.-w-phase trans-
formation (292). Thermodynamic potential (295). Inhomogeneous
states (296).
References . . . . . 298
Chapter 9. Incommensurate Periodicity Phases 301

34. General Approach to the Problem . . . . . . . 301
Commensurate and incommensurate phases (301). Expansion of a
thermodynamic potential with continuous order parameters (303).
35. Phases without Linear Gradient Terms in Free Energy . . . . . . 304
One-component order parameter (304). Two-component order pa-
rameter (309). Three-component order parameter (311). Lifschitz
point (316).
36. Phases with Linear Gradient Terms 318
The soliton lattice (318). Soliton lattice stability (323). The devil's
staircase (328). Stochastic regime (331).
x CONTENTS
37. Multi-K-structures 332

Conditions for many-arm structures to be thermodynamically favor-
able (332). Multi-K-structure in CeAl 2 (334). Multi-K-structure in
Nd (336).
38. Incommensurate Phases in External Fields 340
Helical structure in an external field (340). Effect of external fields
on the wave-vector of incommensurate phases (343).
39. The Thermodynamics of Phase Transitions to Incommensurate
Phases . . . . . . . . . . . . . . . . . . . . . . . . . 347
Constructing a thermodynamic potential for non-Lifschitz stars
(347). Phase transition from incommensurate to commensurate phase
(350). Concomitant order parameters and incommensurate-phase
symmetry (351). Peculiarities of susceptibilities in incommensurate
phases (353).
References . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
Chapter 10. Color Symmetry and its Role in Phase Transition

Theory. . . . . . . . . . . . . . . . . . . . . . 358
40. Color Symmetry in the Theory of Magnetic Structures . . . . . . 358
Magnetic structures and their symmetries. Geometric aspect (358).
Color symmetry and the thermodynamic-potential model (360). The
hierarchy of approximations for describing the magnetic structure of
FeGe2 (362).
41. Supersymmetry of Incommensurate Structures 365
Incommensurate structures and the paradox of the Cheshire cat
(365). Phase symmetry of the thermodynamic potential and the sym-
metry of incommensurate structures (367).
42. Icosahedral Symmetry of Crystals. Quasicrystals . . . . . . . . . 372
A new type of atomic ordering (372). The geometric aspect (374).
The thermodynamic aspect (379). The symmetry of quasicrystal
structures (385). A186Mn14: A Fibonacci structure or a quasicrys-
tal? (387). Conclusion (388).
43. Color Groups in the Theory of Systems with a Quantum Mechanical
Order Parameter 390
The quantum mechanical order parameter (390). Classification of
ordered phases on the basis of color sub-groups of the normal-phase
CONTENTS Xl
symmetry group (391). OP symmetry and the behavior of the gap

in K space (394). Thermodynamic potentials (399).
References . . . . . . . . . . . . . . . . 401
Chapter 11. Fluctuations and Symmetry 404

44. Fundamentals of the Fluctuation Phase Transitions Theory 404
Critical indices (404). The renormalization-group and (-expansIOn
method (406). The isotropic model (413).
45. Critical Behavior of Anisotropic Systems . . . . . . . . . . . . 415
Universal classes (415). Cubic anisotropy (417). Examples of systems
with multicomponent order parameters (419).
46. Fluctuation-Induced Break-Down to First-Order Phase Transitions. 423
The absence of stable fixed points (423). First-order transitions in
magnetic systems (424).
47. Fluctuations in the Vicinity of Multicritical Points . . . . . . . . 426
Systems with coupled order parameters. Bicritical and tetracritical
points (426). Lifschitz point (434).
References 437
Appendix 439
Index . . 441
Preface
About half a century ago Landau formulated the central principles of the phe-
nomenological second-order phase transition theory which is based on the idea
of spontaneous symmetry breaking at phase transition. By means of this ap-
proach it has been possible to treat phase transitions of different nature in
altogether distinct systems from a unified viewpoint, to embrace the aforemen-
tioned transitions by a unified body of mathematics and to show that, in a
certain sense, physical systems in the vicinity of second-order phase transitions
exhibit universal behavior.
For several decades the Landau method has been extensively used to an-
alyze specific phase transitions in systems and has been providing a basis for
interpreting experimental data on the behavior of physical characteristics near
the phase transition, including the behavior of these characteristics in systems
subject to various external effects such as pressure, electric and magnetic fields,
deformation, etc.
The symmetry aspects of Landau's theory are perhaps most effective in
analyzing phase transitions in crystals because the relevant body of mathemat-
ics for this symmetry, namely, the crystal space group representation, has been
worked out in great detail. Since particular phase transitions in crystals often
call for a subtle symmetry analysis, the Landau method has been continually
refined and developed over the past ten or fifteen years. A general survey of
the various trends in the evolution of Landau's theory in the past two decades
is presented at the end of §l. The object of the present book is to provide an
exhaustive account of the current state of Landau's theory of phase transitions
as applied to crystals. The particular physical nature of a phase transition itself
is of no fundamental importance, since the various (structural, magnetic, ferro-
electric, and other) transitions are described in terms of a unified scheme based
on the mathematical foundations of the theory of space group representations.
XIII
XIV PREFACE
A special challenge to the authors was the exposition of methods that

permit analysis of phase transitions in crystals of arbitrary complexity. In
keeping with this goal, efficient techniques are handled and developed in this
book allowing one to determine the principal characteristic of a system under-
going a phase transition, that is, the order parameter, from a knowledge of
the symmetry groups of the initial and final phases, or to enumerate all the
symmetry-allowed phases that are likely to arise as a result of a second-order
phase transition from the initial phase. Methods are presented of constructing
polynomial expansions of the thermodynamic potential in powers of a multi-
component order parameter. The exposition of the general theory and methods
is illustrated with numerous examples of typical phase transitions of different
nature, so that the reader may learn independently to apply this material in
practice. This is facilitated also by a number of tables compiled by the authors,
which furnish in compact form the necessary information related to irreducible
representations of space groups.
Some chapters of the book deal with the analysis of phase diagrams in the
space of thermodynamic-potential parameters and in the space of generalized
thermodynamic forces. Consideration is given to the most important thermo-
dynamic potential types, and the analysis performed in the book shows what
kind of physical effects may be expected to occur in specific, more complicated,
cases and what devices should be invoked to accomplish such an analysis.
Along with the exposition of general methods, the book provides an over-
view of recent developments in a number of new branches of the physics of phase
transitions, such as transitions to incommensurate phases, and the branch con-
cerned with the role of fluctuations.
Thus the present book combines and gives a sufficiently detailed treatment
of both major constituents of the contemporary phase transition theory -
symmetry theory and fluctuation theory. By doing so, the authors have tried
to show how the underlying suggestion by Landau that second-order phase
transitions display a universal symmetry-governed behavior has been revived
in fluctuation theory as the universality of the critical indices, which depend
only on the number of components of the order parameter, that is, ultimately
on symmetry again.
Taking into account the systematic and fundamental character of presen-
tation, it is hoped that the sophisticated reader will find in the book a general
and fairly exhaustive treatment of a large domain of the theory of phase tran-
sitions in crystalline systems, as well as some new techniques of symmetry
PREFACE xv
analysis at a phase transition. As for the reader who has just started studying
phase transition theory, he will be able to master methods of analysis and to
learn how to apply these in solving particular problems. The reader who is
unconcerned with the mathematical machinery of phase transition theory and
wishes only to become acquainted with the most fundamental results of the
theory is recommended, on reading the first introductory chapter of the book,
to start reading the last four chapters.
The authors wish to express their sincere appreciation to Prof. I.E. Dzyalo-
shinsky for his support of the idea to write this book, for the numerous bits
of advice as to the selection of the topics involved, and for the criticism and
discussions that have helped to improve the text.
Preface to the English Edition
Nearly five years have passed since the Russian edition of the book appeared.
In this time span some problems of the phenomenological theory of phase tran-
sitions in crystals have been the subject of intensive research and have evolved
into new independent provinces. Three major areas have arisen: the theory
of reconstructive phase transitions, aspects associated with the exploitation of
color symmetry, and the theory of incommensurate structures.
It is these new areas of research activity that have received considerable
attention in the present English edition (Chapters 8-10). Chapters 8 and 10,
dealing with reconstructive transitions and color symmetry, have been writ-
ten especially for the English edition. Chapter 9, devoted to incommensurate
structures, has been substantially revised and enlarged.
Chapter 8 treats martensitic phase transitions from the b.c.c. to the f.c.c.
and h.c.p. phases. These transitions are certainly first-order transitions and
go without the group-subgroup relation. However, a decisive role in these
transitions attaches to strains, from which one may construct the order param-
eter and use the expansion of the thermodynamic potential in powers of it, in
the spirit of Landau's second-order phase transition theory. In describing the
transition itself and the characteristic pretransient phenomena, an important
role pertains to inhomogeneous states, which are soliton solutions of non-linear
equations of elasticity theory. Chapter 8 provides a systematic review of recent
developments in the problem of martensite transformations.
Chapter 10 treats a set of phase transitions whose description calls for
color symmetry. Here belong transitions to incommensurate structures and
quasi crystals and also phase transitions in systems described by a quantum
mechanical order parameter. Traditionally, color symmetry is used to describe
and classify structures. This chapter lays emphasis on the more important
physical meaning of the color groups as a mathematical machinery that enables
one to ascertain the role of physical interactions responsible for the occurrence
xvii
xviii PREFACE TO THE ENGLISH EDITION
of specific structures. Consideration is given also to another aspect of color

symmetry, the so-called color supersymmetry - the symmetry of multidimen-
sionallattices, in terms of which a generality of commensurate-incommensurate
and melt-quasicrystal transitions is established. Section 20 contains a new sub-
section that deals with orientational phase transitions, and the bibliography of
Chapter 1 has been supplied with fresh references.
It is hoped that the enlarged English edition of the book contains a prac-
tically complete up-to-date exposition of problems in the theory of phase tran-
sitions in crystals, which is based on the concept of the order parameter and
on symmetry.
Most sincere thanks are due to Prof. A. Janner and Prof. J. Birman who
have recommended including in the English edition many of the above prob-
lems, and also we would like to express our sincere gratitude to Dr. D.J. Lamer
who has given us an opportunity, on behalf of the D. Reidel Publishing Com-
pany, to introduce the aforementioned additions. For technical assistance in
preparing the English manuscript, we would like to thank Vyacheslav Reprint-
sev.
Yuri Izyumov
Vladimir Syromyatnikov
Notation
G crystal space group

wave-vector group
space group element with h its rotational part and T hits
accompanying translation
arbitrary integral translation of the crystal
arbitrary reciprocal-lattice vector
primitive reciprocal-lattice vector
wave-vector
wave-vector star
star arm
number of star arms
gL representative element of the decomposition of group G" relative
to a subgroup
d"V wave-vector group irreducible representation
Iv dimension of the representation
DHv space group irreducible representation
d; permutational representation of group
d~, mechanical representation of group
d'Xl magnetic representation of group
T irreducible representation of group G" according to Kovalev's
tables
irreducible-representation basis function
mixing coefficients of the basis functions of an irreducible
representation
TJ).. or 6 order parameter component
n number of order parameter components
phase of the complex order parameter
thermodynamic potential
xix
xx NOTATION
r coefficient of a quadratic expansion term

up coefficients of quartic expansion terms
8 coupling coefficient of the concomitant and leading order
parameters
CHAPTER 1
Introduction to Phenomenological Phase

Transition Theory
1. Fundamentals of Landau's Thermodynamic Theory
ELEMENTARY THERMODYNAMIC ANALYSIS
The behavior of the various systems in the vicinity of second-order phase transi-
tions can be understood on the basis of the order parameter concept introduced
by Landau [1,2]. The order parameter (OP) TJ specifies a new physical property
that arises in a system as a result of a phase transition from the initial phase in
which this property was absent. Thus the OP TJ is defined so that TJ is equal to
zero on one side of the phase transition and is finite on its other side. Since the
phase transition at the transition point To itself is continuous, the OP TJ = 0
and increases monotonically in moving away from this point.
In the vicinity of the phase transition point the thermodynamic potential
~, which depends on temperature T and generalized forces X, should be char-
acterized also by the value of the OP and may, by virtue of its smallness in this
vicinity, be expanded in a power series of TJ. As is well known currently [2], this
expansion holds in the vicinity of To, except for the narrow interval near the
phase transition point itself, where OP fluctuations play an important role. On
the assumption that we are outside this interval, we represent the expansion as
(1.1)
where ~o is the value of the potential in the initial phase and r, v, u are certain
parameters of the system dependent on T and X.
1
2 CHAPTER 1
The equilibrium value of the OP is determined from the requirement that

 as a function of
7} be minimum and is found from the two relations
0<1> = 0, (1.2)
017
0 2<1>
07}2 > O. (1.3)
Equation (1.2) clarifies why the expansion (1.1) involves no linear term in 7}.
We adduce the major arguments of Landau's theory: For the equilibrium

value of 7} in the initial phase (at T> To) to be equal to zero, it is necessary
that l' > 0; on the other hand, for a non-zero 7} to occur for T < To, it is
required that l' < O. Therefore at the phase transition point l' = O. In the
vicinity of To the coefficient of the quadratic term involved in the expansion of
 may thus be expected to be a linear function of temperature
l' = r~(T - To) + .... (1.4)
We start by considering the case where the coefficient v is identically equal

to zero. For such phase transitions the condition (1.3) for stability at the phase
transition point itself gives
u > O. (1.5)
It will be assumed that in the vicinity of the phase transition the coefficient
u is positive for any T and that 1> reverses sign in accordance with the law (1.4).
Under these conditions the occurrence of a finite value of the OP 7} becomes
thermodynamically favorable. Indeed, equation (1.2) may be rearranged in the
form
(1.6)
whence it follows that two real-valued solutions of this equation exist: 7} =0

for T > To and
7} =
-1') 1/2 ,. . , (To -
(2u"" T)1/2 (1.7)
for T < To. Thus the temperature T = To is the branch point of the solution of
the OP equilibrium-value equation. Implying the T and X dependence of the
quantities l' and u, we will call this equation an equation of state. The situation
of interest is depicted also in Fig. 1.1, where the occurrence of finite OP values
for T < To is described by the appearance of thermodynamic potential minima.
PHENOMENOLOGICAL PHASE TRANSITION THEORY 3
T>Ta T< To
Fig. 1.1. Thermodynamic potential in the vicinity of the second-order

phase transition.
T
o
Fig. 1.2. Temperature dependence of the order parameter m the
thermodynamic theory of second-order phase transitions.
VVe see how Landau's simple arguments lead to the fundamental result
(1.7) that the OP is temperature dependent (Fig. 1.2) near the second-order
phase transition. vVe emphasize that this result applies to the case where the
expansion of the thermodynamic potential in powers of the OP contains no
cubic term in TJ. Now we expressly consider the case where such a term is
present and verify that it gives rise to a first-order phase transition when the
continuity at the transition point is broken and an OP discontinuity arises.
We write down the equation of state (1.2) for the expansion (1.1) including
the cubic term
(1.8)
There are two non-zero solutions:
3v
18u 12 - ~
3v
TJ± = --± 2u'
(1.9)
8u
which will be real at a positive discriminant, that is, when
r ::; 9v 2 /32u. (1.10)

4 CHAPTER 1
These solutions as a function of r, that is, temperature, are presented in Fig.

1.3. The symmetry of the 1](r) curve with respect to the r axis corresponds to
the invariance of the equation of state under the substitution v ---+ -v, 1] ---+ -'f}.
Fig 1.3. Solutions to the equation of state (1.8) in the presence of

a cubic term in <1>. The dashed ('f) = 0, r = 0) curve refers to a
second-order phase transition for v == O. The symmetry of the 17( r)
curve with respect to the r axis corresponds to the invariance of the
equation of state under the substitutions v ---+ -v and 1] ---+ -'f}.
The ambiguous behavior ofthe OP in the temperature range corresponding

to the interval r between the points A and B indicates that the state with
the corresponding OP values is unstable. For r > r A = 9v 2 /32u a non-zero
OP value is impossible; therefore, the point r = r A defines the boundary of
absolute instability of the ordered phase. On the other hand, the value r = 0
evidently corresponds to the absolute instability boundary of the disordered
(initial) phase with 1] = O. The above bounds on the values of r determine two
temperatures
9v 2
=
TA To + -32I ' TB To,
ttro
= (1.11)
TA being the superheating temperature of the ordered phase and TB the su-
percooling temperature of the disordered phase (we assume that the ordered
phase exists at higher temperatures than the disordered phase).
A true phase transition occurs at temperature TB < Te < TA. The value
r = re that corresponds to Te and the equilibrium OP value 'f} = 'f}e are found
by simultaneously solving the equation of state (1.8) and from the equality of
the thermodynamic potentials in the ordered and disordered phases
(1.12)
This gives the value of the phase transition temperature and the value of the
OP jump at the transition point
v2
Te = To - - 4I '
uro
1]e = - -.
V
2u
(1.13)
It can be readily verified that the resulting 1]e value corresponds to the largest
(in magnitude) of the two possible OP values for r = re (Fig. 1.3). The state
with the smallest 1]e value has the largest energy and is therefore metastable.
We have arrived at the conclusion that the presence of a cubic term in
the expansion of makes the phase transition a first-order phase transition.
A second-order phase transition occurs in systems where the coefficient v of
the cubic term is identically equal to zero. As will be seen in the section
that follows, this may be dictated by symmetry considerations. However, if
one allows for the fact that all thermodynamic potential expansion coefficients
depend not only on temperature, but also on generalized forces, it may turn
out that at some point (Te, Xc) the coefficients r and v go simultaneously to
zero. At that point, determinable from the system of two equations,
(1.14)
the phase transitions will be of second order. But that will be an isolated
point in the phase diagram on the (T, X) plane, whereas for a system with
v == 0 there is a phase transition line Te = Te(X) which is determined from one
equation,
(1.15)
If there are several generalized forces X, then one should certainly talk of some
surface in the space of temperatures and all generalized forces X rather than
a phase transition line. Instead of the isolated point of equations (1.14), it is
then possible to determine some line or surface of lower dimensionality.
We conclude this elementary thermodynamic analysis by determining the
regions of stability of the ordered and disordered phases in the space of the
potential parameters r, v, u, . ... We wish to specify concretely the stability
regions on the (r, u)-plane at fixed values of v. Thus at v = 0 we have, by
virtue of the foregoing, a simple phase diagram such as that sketched in Fig.
1.4. For involving a cubic term, the situation described above is illustrated
by Fig. 1.5. The solid line refers to first-order phase transitions; it corresponds
to the solution
v2
r = re = - (1.16)
4u
6 CHAPTER 1
of the equation of state (1.8) and the energy equality (1.12) of the two phases.
The dot-and-dash line is the boundary of stability of the ordered phase, ob-
tained from the condition (1.3). This boundary is determined by the equation
9v 2
1'= - (1.17)
32u
and coincides with the boundary (1.10) of existence of real solutions to the
equation of state. Stable states are those with 'fJ f. 0, which correspond to the
region lying below the dot-and-dash curve. On the other hand, it follows also
from the condition (1.3) that the stability region of the phase with 'fJ = 0 is
defined by the inequalities l' > 0 and u > O. Consequently, the stability regions
of the phases with 'fJ = 0 and 'fJ f. 0 overlap on that part of the plane that
is bounded by the dot-and-dash curve and the abscissa axis. The region of
overlap corresponds to metastable states, t.he first.-order phase t.ransit.ion curve
passing within t.his region. When v -+ 0 Fig. 1.5 transforms into Fig. 1.4.
r
LI
Fig. 1.4. Phase diagram in the absence of a cubic term in the ex-
pansion of the thermodynamic potential. v = 0, phase with 'fJ = 0; 'fJ,
ordered phase with order 'fJ f. O.
r
\
\.71=0
'-.'-.....-
u
Fig. 1.5. Phase diagram in the presence of a cubic t.erm in the expan-
sion of the thermodynamic potential.
The analysis performed applies to a phase transition that is character-

ized by a one-component OP. In the general case the OP is a multicomponent
quantity, 1] = {1]1, 'fJ2,·· .}, and to analyze a phase transition, it is necessary
to expand the thermodynamic potential in powers of all of its components.
Symmetry considerations playa dominant role in constructing the shape of the
potential.
SPONTANEOUS SYMMETRY BREAKING AT A CONTINUOUS PHASE TRANSITION
Landau was the first to pay attention to the fact that at any second-order phase
transition a symmetry change occurs in the system. Let the initial (more
symmetric) phase be specified by the symmetry group G, which leaves the
macroscopic density function p(1') of the system invariant. The density function
may be scalar, vector-valued, tensor-valued, etc., according to the physical
meaning of the quantity varying at the phase transition.
Since the state changes continuously at second-order phase transitions,
the symmetry of the new phase may lower only due to the loss of part of the
symmetry elements and will be described by a group G 1 that is a subgroup of
the initial group G. Mathematically, this may be represented as
(1.18)
Each low-symmetry phase will be called a dissymmetric phase and de-

scribed by the density function p(1') = po(1') + 8p(1'). The method of analyzing
symmetry changes at a second-order phase transition, proposed by Landau, is
based on expanding the density function p(1') or 8p(r) in a complete set of ¢;A (1')
functions transforming according to the irreducible representations (IR's) D V
of the initial group
8p(1') = 2: 2: CX¢;A(1'), (1.19)
v A
where CX is an expansion coefficient which is independent of coordinates but

varies with temperature. In the symmetric phase (as a rule, at T > To) all the
CX = 0, but when T < To at least some of these coefficients should be non-zero.
Since the density function varies continuously at the phase transition point as
T ----> To, the coefficients CX tend to zero and may be considered small in the
vicinity of To. Therefore, it suffices in the expansion of the thermodynamic
potential <P in the vicinity of To in a power series of CX to restrict attention to
the first expansion terms. The expansion begins with quadratic terms in the
8 CHAPTER 1
coefficients CA and may be written in the form
<1> = <1>0 + 2:>'v L(CA)2 + .... (1.20)

v A
From the condition that <1> be minimum, it follows that the linear terms in
this expansion cancel out. The structure of the quadratic terms is determined
by the fact that only one second-order invariant ~A (CA)2 exists for each IR
D V according to which the quantities CA transform under the action of the
group G elements. Higher-order (cubic, fourth-order, etc.) expansion terms
are invariant polynomials of the corresponding order; they may be found for a
given group G using familiar mathematical recipes.
With regard to the expansion (1.20) one may apply the same lines of argu-
ment as those that we have used in the elementary Landau analysis outlined in
the beginning of this section. The quantities rV depend on temperature and ex-
ternal forces through the generalized thermodynamic quantities X. At T > To
all the rV should be positive, so that the equilibrium value of the parameters
C A is equal to zero. If one of the quantities rV at T < To becomes negative,
the occurrence of a state with a finite value of CA, that is, the appearance of
a dissymmetric phase, is energet.ically favorable. As the temperature is varied
several quantities may, in principle, vanish one after the other; however, the
temperature T = To at which one of the quantities rV goes to zero for the first
time is the phase transition temperature. This temperature is determined from
the equation
(1.21)
The corresponding IR D V is said to be responsible for the phase transition.

At T < To at least one quantity CA involved in the set of quantities [CAl
pertaining to the responsible representation is non-zero, and all the CAfor the
other IR's may be set equal to zero. In this case the expansion (1.20) for the
thermodynamic potential reduces to
<1> = <1>0 + r L 1]X + ... , (1.22)

A
where the CAfor the responsible representat.ion D V is labelled 1]A and the index
of this representation is omitted. Accordingly, the density function (1.19) of
the dissymmetric phase is expressed also only in terms of the quantities
8p(r) = L 1]A9;\(r). (1.23)

A
It is the mixing coefficients 1JA of the basis functions of the responsible IR that
are called order parameter components; the number of these components is
equal to the dimensionality of the responsible IR. This definition is a general-
ization of the order parameter 1J concept originally introduced by Landau. The
equilibrium value of the order parameter components is determined from the
requirement that the expansion (1.22) be minimized with respect to 1JA and
specifies the dissymmetric phase density function (1.23).
Equations (1.22) and (1.23) express the hypothesis by Landau that a phase
transition should occur according to one IR. It may happen, however, that in
the expansion (1.20) it is not one, but two coefficients rV at once that may go
to zero at T = T c , for example for the IR's Dl and D2. The equations
(1.24)
define not the phase transition line Tc = Tc(X), as in the case (1.21), but
the point (Tc, X c). In the vicinity of this point it is necessary in the thermo-
dynamic potential expansion (1.20) to retain the coefficients CX for both IR's.
The situation described corresponds to the case of interacting order parameters.
Both IR's are responsible in this situation, so that at the point (Tc, X c) itself the
phase transition occurs according to a reducible representation of the symmetry
group of the system. The dimensionality of the total OP at the point (Tc, X c)
increases. This additional degeneracy may be accidental (as the crossing of two
lines (1.24) on the (T, X)-plane) or due to special symmetry considerations.
THE LANDAU CONDITION FOR A SECOND-ORDER PHASE TRANSITION
The general scheme of Landau which we have outlined above enables one to
find all admissible dissymmetric phases liable to arise from a given phase via
a second-order phase transition. The corresponding analysis reduces to the
construction of an expansion of the thermodynamic potential in powers of the
OP transforming according to an IR of some group G, followed by minimization
of the potential.
Landau has solved, in general form, the problem as to which of the initial-
group IR's cannot give rise to a second-order phase transition [2]. As was
clear from the first subsection, the presence in the thermodynamic potential
of cubic terms leads inevitably to a first-order phase transition. Therefore,
the condition [1] which restricts the list of IR's describing the second-order
phase transition consists in the requirement that the IR allow no third-order
invariants. Since the third-order quantities constituted by the coefficients CX
10 CHAPTER 1
transforming according to the IR D V themselves transform as a symmetric cube

of this representation, the condition for the absence of third-order invariants
is that this represf'ntation contains no group G identity representation Dl.
Mathematically, the condition formulated can be written in the form
(1.25)
The standard notation is used here: [D V3 ] denotes a symmetric cube of repre-

sentation D V and:::> is the inclusion symbol (;;6 the exclusion symbol).
FURTHER DEVELOPMENT OF LANDAU'S THEORY
The original Landau theory assumed the dissymmetric phase arising from the
phase transition to be homogeneous. Lifschitz [3,4] demonstrated that for spa-
tially inhomogeneous phases to occur, it is necessary that the thermodynamic
potential involve terms containing OP derivatives with respect to the coordi-
nates. Linear invariants in derivatives came subsequently to be called Lifschitz
invariants (their role in phase transition theory will be discussed in detail in
Chapter 8).
Following Landau and Lifschitz's fundamental writings and a rigorous
group-theoretic exposition of those papers in the book by Lubarskii [5], a fur-
ther basic step in the development of phase transition theory was made by
Dzyaloshinsky [6,7] who constructed a theory of incommensurate phases in
crystals with reference to the example of long-period magnetic structures. He
was the first to show that the various modulated phases in crystals may be
obtained as a solution of the non-linear differential equation that results from
minimization of a thermodynamic potential comprising OP gradients. The non-
linear differential equation coincided with the mathematical pendulum equa-
tion, and analysis of its solutions led to a soliton picture of the incommensurate
to commensurate phase transition. It was noted also by Dzyaloshinsky that
the wave-vectors of incommensurate phases actually possess different symme-
try (with the wave-vector length varying along a fixed direction), a fact that
leads to a sequence of modulated-phase transitions giving rise to intermediate
commensurate phases. This array is currently known as the "devil's staircase",
the name having already become rooted in the literature. The theory of incom-
mensurate phases was further evolved by Ishibashi [8], Dvorak [9], Bak [10],
Levanyuk [11], and Sannikov [12].
Over the past two decades the Landau theory has been developing in two
directions - evolving the physical picture of phase transitions and working out
PHEN01VIENOLOGICAL PHASE TRANSITION THEORY 11
mathematical techniques of the theory. Thus various particular phase transi-

tions in complicated systems have been studied on the basis of investigations
into the multicomponent 0 P's (Dzyaloshinsky [13], Indenbom [14], Levanyuk
and Sannikov [15-17], Dvorak [18], Aizu [19]); the important concept of the
paraphase has been introduced to account for the symmetry coupling of the
phase transition array observed ill materials of current interest (Levanyuk and
Sannikov [20,21]' Aizu [22], Dvorak [23]). Finally, relying on the celebrated
Curie principle, specific relationships have been established between the phase-
transition-induced physical prolwrties and the crystal symmetry (Indenbom
[24]), notably for the crystal's domain structure (Zheludev, Shuvalov [25,26]'
J anovec [27]).
Two trends should be singled out in the development of mathematical

methods. One area of research activity dates back to Birman [28] who pro-
posed a novel scheme of searching for dissymmetric phases with a given wave-
vector that arise from a given phase of the symmetry group G. Rather than
find the mixing coefficients of basis functions from thermodynamic potential
minimization equations, he suggested analyzing the list of all subgroups G 1 of
the group G and the list of all IR's of the group G with a given wave-vector.
There exist simple group-theoretic criteria [28,29,30] that permit selection of
admissible subgroups and admissible IR's under which the phases sought are
liable to arise. Valuable features of this method are that, first, it enables one, in
principle, to find all phases; second, the result of applying the method does not
depend on the degree of approximations in the thermodynamic potential; and
third, this method allows the tedious minimization procedure to be averted.
The other trend, developed by Gufan [31-33], is associated with probing

the phase transition in the OP space. The most essential concept here is the
IR image group (I-group), an assembly of various IR matrices. Revealing the
I-group permits one to find what we call the integral rational basis of invariants
according to which a polynomial representation of a thermodynamic potential
of any degree can be readily constructed. It turns out that different IR's (of
specified dimensionality) in altogether distinct space groups may have identical
I-groups, therefore such systems refer to the same thermodynamic potential.
In all of these systems the phase transition should behave in the same way irre-
spective of the nature of the OP. The body of I-groups is thus a mathematical
machinery indicating a universality in the physics of phase transitions, and it is
primarily this circumstance that makes the I-groups fundamentally important
in phase transition theory. A substantial contribution to the disclosure of this
12 CHAPTER 1
fact has been made by Toledano [34], Michel [35], and Kopsky [36].
The above trends of the phenomenological phase transition theory were
based on the utilization of crystal space groups. Recently a new trend has
arisen which employs color groups (Wolf [37]; Janssen, Janner [38,39]; Litvin,
Kotzev, Birman [40]). The mathematical machinery of the color groups has
proved convenient in describing magnetic phase transitions [40], incommensu-
rate phases [37-39], and also quasicrystals [41].
The aforementioned trends in the development of the Landau theory dis-
regard the fluctuations, so the conclusions of these theories hold good outside a
narrow vicinity of the phase transition boundaries established by Ginzburg [42]
and Levanyuk [43]. In considering the role of fluctuations that exist within the
critical region, it is also very helpful to exploit the mathematical machinery of
the I-groups.
The present book expounds the major trends in the development of the
Landau theory and outlines the contemporary status of the phenomenological
treatment of phase transitions in crystals and the current state of the theory's
working methods.
2. Prerequisites on Space-group Representations
SPACE-GROUP IRREDUCIBLE REPRESENTATIONS
As the present book deals with phase transitions in crystals, the theory's math-
ematical background rests on space group representations. Assuming a certain
mathematical sophistication on the part of the reader at a level of Landau and
Lifschitz's course [2], we restrict ourselves in this section to the most impor-
tant information from space group representation theory needed for the further
exposition. A more detailed treatment of the theory of the space groups them-
selves and of their representations can be found in many books, of which the
reader is recommended to refer to the monograph [44] where the notation em-
ployed is the same as that adopted here.
The space group IR's are specified by wave-vectors defined with the help
of reciprocal crystal lattice vectors. Labelling the primitive translation vectors
by t 1 , t 2 , t 3 , the primitive reciprocal lattice vectors b l , b 2 , b 3 are defined, as
is known, by the expressions
Va = [tl x t 2] . t3 being the volume of a primitive cell of the crystal. If

the bulk of the crystal is chosen as a parallelepiped constructed on vectors
Nlt l , N2t2, N3t3 (Nl' N 2, N3 are large integers), the wave-vector is defined
by the quantity
(2.2)
where Pl, P2, P3 are integers that satisfy the conditions 0:::; Pi :::; N - 1. Thus
the expression (2.2) defines N admissible wave-vector values, N = N1N2N3
being the number of primitive cells in the bulk of the crystal. All the wave-
vector values thus defined lie in the primitive reciprocal lattice cell.
The construction of IR's of a space group G is associated with the action
of its elements 9 on a given wave-vector",. Some of the elements of group G
leave the vector", invariant or transform it into an equivalent one (which differs
by an arbitrary reciprocal lattice vector b). The totality of all such elements
satisfying the condition
(2.3)
forms a subgroup G" of group G and is called the wave-vector group. The
group G" thus specifies the intrinsic symmetry of the wave-vector ",. All the
wave-vectors that differ in symmetry and all the G" groups corresponding to
them are tabulated in special reference books [45,46]. Of these, we shall make
use of the manual by Kovalev [45].
The IR's of the wave-vector group G" are characterized by the wave-vector
", and the representation number II. Representation matrices d"v (g) for group
G" elements should be taken from tables, for example [45], where they are
written out only for group G" zero-block elements, that is, elements that contain
no integral translations t. \Ve denote space group elements 9 by the symbol
9 = {hlTh + t}, with h the rotational part of the element, Th an accompanying
fractional translation, and t an arbitrary integral translation. The IR matrices
for any group G" element are expressed in terms of zero-block element matrices
by the equation
(2.4)
The IR's of the entire space group G are characterized by a \"ave-vector
star, which is labelled {",}. One calls a star a set of non-equivalent wave-vectors
that are obtained from a given wave-vector by the action of all the space group
elements, and the individual vectors comprised in this set are said to be star
arms, "'L. The latter can be obtained by the action of gL elements on a given
wave-vector ",:
(2.5)
14 CHAPTER 1
these elements being representative elements of the coset decomposition of

group G relative to its subgroups G,,:
(2.6)
The number of star arms I" is evidently equal to the index of the subgroup G"
in the group G and does not exceed, for all the space groups, forty-eight - the
maximum number of elements in the crystal point groups.
Equation (2.6) allows one to construct matrices D{"}v (g) of the IR's of
the space group G from the group G" ofIR matrices d"V(g). The dimension of
these matrices will obviously be lvi,,, with Iv the dimension of the IR d"V. The
relation between these is given by the equation
g"L 1ggM E G"

D L)..,Mp.
{"}V ( )
g = d"v (-1
gL ggM
)..p.
){ 1,
0,
g"L 1 ggM rt. G".
(2.7)
Here A, J1. = 1,2 .. . Iv are the matrix indices of the representation d"v, Land M
denote the numbers of the representatives in the decomposition (2.6) and, at
the same time, are the numbers of the star arms. Thus, taking the wave-vector
group IR matrices from tables [45,46], formula (2.7) enables one to obtain the
matrices of the appropriate IR of the entire space group.
The basis functions of the group G" IR are Bloch functions of the form
(2.8)
where the u~V(r) are periodic functions with respect to crystal translations.
Under the action of a group G" element the set of 1jJ~v (A = 1,2, ... , Iv) trans-
form according to the equation
Iv
g1jJ~v =L d~>" (g )1jJ~v. (2.9)
p.=1
A basis of the IR of the entire group G is generated by the set Inlv of Bloch func-
tions {1jJ~lV}, {1jJ~2V}, ... , {1jJ~I"V} prescribed on all star arms "'1,"'2, ... ,"'L,
... , "'1". These functions transform under the action of a group G element g
by means of the equation
(2.10)
In the section that follows we will show in what fashion one should con-
struct basis functions of a crystal space group IR from physical quantities
specifying the state of a crystal after a phase transition. The method rests on
the familiar group theoretic formula for the projection operator [5]
(2.11)
whose action on an arbitrary function from some space yields the function
(2.12)
which transforms according to the IR D Y of the group G. In equation (2.11)

and henceforth the symbol IIGII denotes the number of G elements. In the
expression (2.12) the index inside the square brackets is fixed. With the J1.
being chosen, we make an exhaustive search for all Iy values of index A to
obtain a complete set of basis functions of a given IR. Passing on to another
J1. value, we are in a position to derive another set of basis functions unless an
identical zero occurs.
IRREDUCIBLE REPRESENTATIONS AND THEIR DECOMPOSITION
One of the central problems in Landau phase transition theory is a thermody-

namic potential consisting of invariant polynomials of the quantities 7]~ trans-
forming according to the IR D Y of the group G. The product of n quanti-
ties 7]~ should transform in the general case according to the representation
D yn == DY x D Y x ... x D Y in which the representation D Y recurs n times.
Being symmetric with respect to permutations of the cofactors, the product of
commuting quantities 7]~ actually transforms according to what is known as
the symmetrized product of the representation D yn , which is normally labelled
[Dyn] [5].
This representation, just as every reducible representation, may be decom-
posed into irreducible representations with the help of the general representa-
tion reduction formulas:
(2.13)
(2.14)
where XV(g) is the character of the IR D V and X(g) IS the character of t.he
reducible representat.ion D.
16 CHAPTER 1
The character [Xn] of the symmetrized representation [Dlln(g)] may be

expressed in terms of the character of the lR DII by the following formula [5]:
(2.15)
The summation here is performed over the various partitions of the number
n = L:s r s qs (rsand qs being positive integers). For the initial value this
formula assumes the specific form
1 1 1
"3 XII (g3) + 2"XIl(g2)xIl(g) + 6Xll
3 3
[XII ](g) = (g),
[XIl4](g) = ~XIl(g4) + ~xll(l)XIl(g)+

4 3
122122 14
+SXIl (g ) + 4XIl(g )X ll (g) + 24Xll (g), (2.16)
Exploiting the concept of the symmetrized product of representations, the

Landau condition for second-order phase transitions may be given another
mathematical formulation. According to the formula (2.14), the condition
(1.26) can evidently be rearranged to read
"L[X Il3 ](g) = O. (2.17)

gEG
Using lR tables it is easy to ascertain from equation (2.17) the activity of

a given lR.
The foregoing information from representation theory is assumed to suffice
for reading the subsequent chapters of the monograph. Any requisite extensions
of the body of mathematics will be provided in the context of the physical
problems treated below.
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39. T. Janssen, and A. Janner: Physica A 126, 163 (1984).
40. D.B. Litvin, J.N. Kotsev, and J.1. Birman: Phys. Rev. B 26,6947 (1982).
41. P. Bale Phys. Rev. B 32,5764 (1985).
42. V.L. Ginzburg: Fiz. Tverd. Tela 2, 2031 (1960).
43. A.P. Levanyuk: Zh. Eksp. Teor. Fiz. 36, 810 (1959).
44. Yu.A. Izyumov, V.E. Naish, and R.P. Ozerov: Neitronografiya Magnetikov
(Neutron Diffraction of Magnetics), Atomizdat (1981).
45. O.V. Kovalev: Irreducible Representations of the Space Groups, Gordon
and Breach (1965).
46. S.C. Miller, and W.F. Love: Tables of Irreducible Representations of Space
Groups and Co-representations of Magnetic Space Groups, Pruett Press
(1967).
CHAPTER 2
Physical Realization of the Order Parameters

at a Microscopic Level of Description
3. Tensor Representation of the Space Group on a Basis of

Localized Atomic Functions
The phase transition from the initial phase of the crystal gives rise to a state
which at the microscopic level may be specified by the occurrence of some
spontaneous property on each atom. This property is described by a scalar, a
vector or a tensor. Thus, for example, a static magnetic moment arises on the
atom in a magnetic phase transition and each atom may therefore be specified
by an appropriate pseudovector. In the case of a structural phase transition
by displacement (displacive transition) it is possible to assign to an atom in
a dissymmetric phase a polar displacement vector with respect to its position
in the symmetric phase; the assignment of the polar displacement vector on
each wholly characterizes this phase. If the magnetic ordering is accompanied
by some structural distortions, two vectors should be specified for each atom
in the dissymmetric phase: the magnetic moment pseudovector and the polar
atomic displacement vector. It is better in such a situation to ascribe to the
atom some tensor of rank two. For an ordering-type phase transition each atom
is characterized by a scalar quantity that represents the relative probability of
occupying determinate positions in the crystal.
In the general case one may talk of the occurrence of a certain tensorial
characteristic on each atom, implying that the scalar and the vector are tensors
of rank zero and rank one respectively. The dissymmetric phase resulting from
the phase transition is assigned by specification of the corresponding atomic
characteristic on each crystal atom, information on these characteristics be-
ing extracted from experiment. In keeping with Landau's idea, the state of
the dissymmetric phase may be characterized by a small number of quantities
19
20 CHAPTER 2
which in their entirety form an 1]-component order parameter. To reveal the

OP in a given dissymmetric phase and to determine the irreducible represen-
tation according to which the transition from the initial phase has occurred, it
is necessary, as follows from equation (1.23), to calculate the basis functions of
the symmetry group irreducible representations of the initial phase. The ba-
sis functions should evidently be constructed from localized atomic functions
of the scalar, vector, pseudovector, and other types, according to what phys-
ical characteristic arises in the dissymmetric phase on every single atom. In
what follows we outline a universal method of constructing such basis functions
allowing for the microscopic crystal structure.
Phase transitions that are specified by macroscopic order parameters such
as the strain tensor call also for other basis functions that allow for the crystal
macrosymmetry only. Such basis functions will be considered separately in
Chapter 6.
CONSTRUCTING CRYSTAL SPACE GROUP REDUCIBLE REPRESENTATIONS
Consider a crystal that contains N primitive cells. Let there be in each cell U'R
identical atoms which occupy the same position in the group G and whose state
in the crystal is specified by an R-component tensor of arbitrary rank. Then
the state ofthe crystal as a whole is described by an RU'RN-dimensional column
that indicates the values of all tensor components on each atom. Let the state
of the crystal be characterized by a definite wave-vector K,. To explore the
transformation properties of such a multidimensional vector under the action
of group G K elements, it is convenient to introduce unit vectors of an RU'RN-
dimensional space:
L:$
¢),.f3 = ~f3 eiKtn , (3.1)
n
where ~f3 is an RU'wdimensional column with all the components equal to zero,
except one, which is equal to unity and corresponds to the jth atom of the zero
cell and to the ,Bth tensor component. The symbol L:~ denotes the direct sum
over all N crystal cells obtained from the zero cell by translations tn.
The <p~f3 are the eigenfunctions of the translation operator, for, by defini-
tion (3.1), the following equation holds:
(3.2)
Thus the functions <p~f3 are Bloch-type functions, and this is precisely what the
assignment of the index K, to them signifies.
MICROSCOPIC REALIZATION OF ORDER PARAMETERS 21
Let us see how the functions 1jJ{f3 transform under the operation of group
G" elements g = {hlt n }. An element of the group G" transfers an atom with
number j and coordinate rj from the zero cell (in the general case) into an
atom with number i of another cell:
(3.3)
which may symbolically be transcribed also as
(3.4)
Besides, the ,B-component of the atomic tensor transforms in terms of the other
a-components according to the tensor transformation law. Thus the result of
the action of the operator T(g) on the function ¢~f3 may be written in the form
T(g)¢~f3 = e-i"aij(g) LD'f!(h)¢~OI, (3.5)

01
D'f! (h) being the tensor transformation matrix under the action of the rota-
tional part h of the element {hlth}. The numbers of the atoms in this case
change according to the relation (3.4).
The vector thus obtained may be resolved in terms of the orbits of the
space introduced and the result may be represented as
T(g)ljJ{f3 =L {dR(g)};OI.j!3¢~OI. (3.6)

;01
This equation specifies the tensor representation dR of the wave-vector group

G". On comparing equations (3.5) and (3.6), we obtain the explicit form of the
matrices of this representation:
(3.7)
where the 8-symbol takes into account the condition (3.4) for the permutation
of atoms under the action of the element g.
The tensor representation matrices have dimension R(J'R x R(J'R and it is
clear that the tensor representation should in the general case decompose into
group G" IR's d"V. Symbolically, this may be written as
(3.8)
22 CHAPTER 2
The multiplicity factor nV of the vth IR is determined by the general reduction

formula
nV = IIG"II- 1 LXR(g)X"V(g), g E G", (3.9)
9
where X"V is the character of the IR d"V and X"R (g) is the character of the
tensor representation. According to equation (3.7), the tensor representation
character may be written as
(3.10)
with
(3.11)
(3.12)
In the expression (3.9), where the summation is carried out over all ele-
ments of the space group G", we may take the sum over the translations, so
that the equation contains only the sum over the group G" elements g per-
taining to the zero block. We label the set of these elements by G~, and the
number of these elements by IIG~II. Instead of the formula (3.9) we will then
have an expression that is convenient for practical calculations. Namely,
nV = IIG~II-l LXR(g)X"V(g). (3.13)

9
We have constructed the tensor representation on the basis of localized

atomic functions. The latter may be employed to construct symmetrized com-
binations that will transform according to the IR involved in the tensor rep-
resentation. It is these combinations that we need for describing the crystal's
states that arise from the initial phase as a result of a phase transition according
to an IR.
To construct basis functions 'l/J';,v of the group G" IR, we may use the
projection operator formula
'l/J~V = N- 1 L d~~(g)T(g)'l/J, (3.14)

9
where d~~(g) is a matrix element of the vector representation d"v, and 'l/J is
some starting function. As the starting function we take the unit vector rP~f3
of the space of RURN-dimensional vectors and determine the action of the
operator T(g) on the unit vector using equation (3.6). Then the expression
(3.14) becomes
L
1/;~V = 2::>h~(g) {dR(g)}ia,ji3tP~a. (3.15)
9 ia
The summation over integral translations may be performed using the explicit
form (3.7) of the matrices dR(g). This leads to an expression which involves a
summation over group G" zero-block elements g E G~ only:
.I.I<V
'1-'>. - L... >'/1-
""'" e-l< aij(g)8',g)
_ ""'" dl<v (g) L... . .Vai3(g)A..ia
R '1-'1<' (3.16)
9 ia
Taking into account the explicit structure (3.1) of the expression for the
vector column tP~a, we represent the basis function 1/;~v in the same form:
1/;~V = LEI) (~v ei"t n , (3.17)

n
where (~v stands for a O'R-dimensional vector column
(3.18)
made up of R-component columns. Each component of this column is evidently

determined by the expression
1/;a (~V Ii) =L d~r/1-1 (g )e-il<aij(g) 8i,g[jlV~[i31 (g). (3.19)

9
The quantity 1/;a(~vli) is the atomic component of the basis function. The
indices /-l, j, and /3, enclosed in square brackets in the expression (3.19), should
be fixed. These indices actually determine some start (initial function) for the
construction of a basis function. An alteration of the initial (starting) function
either gives rise to a new system of basis functions (for the cases where a given
IR dl<v is contained more than once in the tensor representation dR ) or leads to
a zero. If the atoms in the crystal occupy several positions of multiple points,
it is necessary in the formula (3.19) to substitute as the index j the number
of one of the atoms of a given position in order to obtain a set of 1/;a(,,/ Ii)
functions for the entire position and then, proceeding in the same fashion, to
obtain functions for the atoms of a different position. For practical calculations
of the expressions (3.19) and (3.13) one has preliminarily to compile a table of
the change in the numbers of the crystal primitive-cell atoms under the action
of the group G I< elements and to find the vectors of the returning translations
24 CHAPTER 2
aij for each atom. The necessary IR matrices are to be taken from relevant
tables (for example, [1]).
THE STABILIZER METHOD
The equations (3.19) and (3.13) are fundamental working formulas by which
one calculates the basis functions describing a phase transition in a crystal. In
actual fact, for the prescribed wave-vector K, and group G" IR d'<l', the formula
(3.19) should be employed to calculate the atomic components 'IjIO'(AVli) for
zero-unit-cell atoms belonging to the same multiple-point position. In doing
so it should be borne in mind that the position of the multiple points of the
parent-crystal space group G with respect to the wave-vector group may split
up into individual assemblies of atoms that transform into each other (to within
integral lattice translations). We call each of these individual totalities an orbit
with respect to the group G". The calculation of the atomic components of the
basis function 1,&0' (A V Ii) for each orbit should apparently be done independently.
To this end, some atom j of a given orbit should be chosen as the start.
In the formulas (3.19) and (3.13) the summation is extended over the
elements of the group G". These formulas, however, may be modified into a
form where the summation is performed only over some of the G" elements,
more precisely those that leave the starting atom fixed. They form what we
call the stabilizer of the space group G". More rigorously and in more general
terms, it is the subgroup H of the space group G that is referred to as the
stabilizer of the space group G; the subgroup H maps a given atom onto itself
(to within integral translations). By transforming the basic formulas (3.13) and
(3.19) in such a way that they contain only the summation over the stabilizer
elements, we substantially facilitate computational work.
Thus we consider some orbit with respect to the group and ascribe to the
starting atom the number j = 1. We denote the stabilizer of the first atom by
H" and decompose the group G" into cosets relative to the subgroup H,,:
(3.20)
The representative element gi evidently transforms the first atom into a number
i atom (gi being the identity element of the group).
To begin with, we transform the phase factor entering into the expressions
(3.11) and (3.19). Recalling the relation (3.3), which serves as the definition of
the returning-translation vector aij(g), we rearrange the aforementioned factor
in the form
(3.21)
ilVe now allow for the fact that the coordinates of any atom of a given orbit
may be expressed in terms of the coordinates of the first atom under the action
of the representative elements rj = gjr1 - aj1(gj), ri = girl - ai1(gi). Using
these expressions and multiplying each vector in the scalar product in equation
(3.21) by g;l, we obtain for the quantity iij(g) two important expressions:
(3.22)
where we have taken account of the fact that g;l", = "', since the element g;l
belongs to the wave-vector group G/<.
Consider now the expression (3.9) which defines the constitution of the
tensor representation. Substitute into it the expression (3.10) for the character
x'R(g) of this representation. Using the notation (3.21) for the phase factor, we
write (g E G,,)
(3.23)
9 j
The o-symbol may be rewritten, using the equation j = gj 1 again, to obtain

OJ,9j = 09j1,99)1 = 01,9;'99)1'
From this it is clear that the element h = gj-1 ggj ,
which leaves the first atom in its site, should belong to the stabilizer H". Thus
the summation in equation (3.23) is actually performed not over all group G"
elements but only over the stabilizer elements. Allowance for the first of the
equations (3.22) yields
nV = IIG"II- 1 L L X"V(h)XR(hhl1(h), hE H".

j h
The sum over j gives the number of atoms in an orbit. This number coincides
with the index of the subgroup H", which is equal to IIG"II/IIH"II. On extending
the summation in the last expression over the translations of the group H", we
write the final expression for nV in the form
nV = IIH211- 1 LX"V(h)Xll(h)XR(h), hE H2, (3.24)

h
where the summation is performed only over the zero block of the stabilizer
group.
26 CHAPTER 2
We now pass on to the expression (3.19) for the IR basis function. 'We re-
turn to the summation over all group G" elements g, rearrange this expression,
and take the first atom (j = 1) to be the starting function:
1/J"(A"li) = N- 1 L>hrI'1(ghi1(g)Oi'91D~[i31(g) (3.25)

9
(we have introduced also the notation (3.21) for the phase factor). We represent
the o-symbol in the form: Oi,gl = 01,g-:-1 g1 , whence it is seen that the element
h = gi 1 g belongs to the stabilizer. 'Thus, just as in the expression for n",
the formula for the basis function contains actually the summation over the
stabilizer elements of the first atom. Removing the o-symbol in equation (3.25)
and using the second of the expressions (3.22), we then write (g E giH,,):
1/J"(~"li) = N- 1 L d~[1'1(ghi1(gihll(gi1g)D~[i31(g).
9
The resulting expression may be worked out (on extending the summation over
the translations of the group H,J to (h E H2):
1/J"(A"li) = 'Yi1(gi) L d~rI'1(gih)D~[i31(gihhl1(h). (3.26)

h
In principle, this result already solves our problem of calculating the atomic
components of the basis function in terms of the stabilizer. However, by passing
on to the matrix representation, a still more convenient formula may be derived
from equation (3.26). The right-hand side of equation (3.26) involves a direct
•
matrix product d""(gih) x DR(gih). Representing each of the matrices as the
product of matrices of individual group G" elements
the expression (3.26) may be written as
(3.27)
where (h E H2)
\Ifl''' = L(d""(h) x DR(h)hl1(h) (3.28)
h
is an I"R x I"R matrix, which should be calculated in advance. To obtain the

basis functions on the ith atom of the orbit, it then suffices to premultiply
* x DR corresponding to the
the matrix \f!~" by the equidimensional matrix d""
element gi. Each non-zero column of the matrix thus calculated gives a basis
function atomic component that transforms by the IR d''''. A total of nV such
columns should be obtained, in keeping with the multiplicity factor of a given
representation included in the tensor representation. Thus the calculation of
the basis functions for all orbit atoms reduces to multiplying the matrices
together, and the calculation of the matrix wi v presupposes summation over
the stabilizer elements only.
The advantage of the formulas (3.27) and (3.28) for the basis function
as compared to the standard expression (3.19) is that it suffices to manipulate
solely with elements of the stabilizer H" and with representative elements in the
decomposition of the group C" relative to H". In these calculations one does
not have to perform the tedious procedure of compiling a table of atomic per-
mutations under the action of all group C" elements and finding the returning
translations aij (g). The stabilizer method has particularly great advantages in
those cases where the number of atoms in the orbit is large and the number of
elements in the stabilizer is, accordingly, small. In this case the matrix w~v is
easy to calculate by the formula (3.28) and calculating the atomic components
of the basis functions reduces to the matrices being simply multiplied together
according to the formula (3.27).
CONSTRUCTING BASIS FUNCTIONS FOR STAR ARMS
In the foregoing we have constructed basis functions for the wave-vector group
IR's. The IR's of the entire space group are realized on a basis that incorporates
basis functions for all arms "'L of the star {"'}. It is of course possible to
construct for each arm independently an appropriate individual basis, using
the formulas derived above. There is, however, a simple method of expressing
basis functions for any star arm in terms of the first arm "'1 alone.
To derive this relation of the basis functions, we recall the equation (2.5),
which expresses the star arm "'L in terms of the arm "'1 : "'L = gL"'L. Ac-
cordingly, the wave-vector group C"L is conjugated to the group C", by the
element gL:
(3.29)
A similar relationship will also exist between their representations and, hence,
between their basis functions:
d"LV(g) = d",V(gLgg"L 1), (3.30)
W~LV = T(gL)W~'v. (3.31)

28 CHAPTER 2
Allowing then for the fact that under the action of the element gL the wave-
vector transforms according to equation (2.5) and the atom changes its number
and cell according to equation (3.4), we can obtain the following expression for
the atomic components of the IR d"LV basis functions:
'f/!"GLV Ii') = e-iI<La;I;(DL) I: Dt (gLW.8(~,V Ii). (3.32)

.8
Here the correspondence between the atom numbers i and i' as well as the
wave-vector ai'i is determined by
(3.33)
4. Permutational Representation and its Basis
A SUMMARY OF FORMULAS
To begin with, we investigate in greater detail phase transitions that are char-
acterized by the occurrence of a phase with a given wave-vector K-, a phase
in which the state of each atom is described by a scalar function. The tensor
representation of the wave-vector group G" given in the general case by the
matrices (3.7) degenerates on a scalar basis into a scalar matrix representation:
( 4.1)
This representation, however, is normally referred to as permutational (this

accounts for the symbol d;(g)), since the action of an element of the group on
an atom reduces solely to a permutation of that atom instead of another atom
in the crystal.
We write for the scalar basis the fundamental formulas of the preceding
section, which permit a reduction of the permutational representation. Instead
of the expressions (3.8), (3.11) and (3.13) we will have in this case
(4.2)
n; = IIG~II-l I:x;(g)X'W(g), g E G~, (4.3)

g
Xp"(g) --~
~ e- i "ajj(g)c5),g).
.. (4.4)
j
The formula (3.19) for calculating the IR basis functions on the arm Ii, then
reduces to
7f>Wli) = Ld~r"l(g)e-i"aij(g)8i'9[jl,9 E G~. (4.5)
9
The formula (3.2) for a basis function on an arbitrary arm li,L (Ii,L = gLIi,) of
the star {Ii,} assumes the form
(4.6)
The permutational representation d; is thus given by (T x (T matrices, where

(T is the number of atoms belonging to a given orbit (in a primitive cell of the
crystal). We also note that the atomic component of the basis function has no
other indices except the index A.
We quote formulas for calculating nil and 7f>(~lIli) according to the stabilizer
method. Instead of equations (3.24), (3.27) and (3.28) we have in the scalar
case
n~ = IIH~II-1 LX"II(h)-Yll(h), h E H~, (4.7)
h
.T,,,II
'J! i = /i1 ()d"l1(
gi
*
gi )'T,"II
'J!1 , (4.8)
W~II = Ld"lI(h)-yu(h),h E H~. (4.9)

h
In what follows we illustrate both methods of computing basis functions,

the standard procedure and the stabilizer method, on a number of particular
examples. The purpose of considering these examples is not only to illustrate
the methods themselves, but also to describe the technique of identifying the
irreducible representation that is responsible for the phase transition.
THE OP FOR ORDERING IN AB TYPE ALLOYS
We start by analyzing the simplest and well-known ordering-type phase tran-

sition in equiatomic two-component AB type alloys (AuCu, CoPt, FePd, etc.).
These compounds form an f.c.c. structure, each lattice site in the disordered
state (T > Tc) being filled equiprobably with A or B atoms. At T < Tc the
probabilities of certain sites being filled with atoms of different sort become dif-
ferent, so that some superstructure arises which is specified by a wave-vector.
When T ---+ 0 some lattice sites are occupied by atoms of the same species only;
this gives rise to a completely ordered structure such as that shown in Fig. 2.1.
30 CHAPTER 2
T> Tc
(a) (b)
Fig. 2.1. Statistic lattice of AuCu type alloys III disordered and
ordered states.
It is a simple matter to see that this ordered structure is described by the
wave-vector
271"
Ii, = -(00 1). (4.10)
a
Indeed, if we locate the origin of coordinates at the position of atom 1, the
translation vectors to atoms 1', 1", I'" will be equal to a(O ~ ~), a( ~ 0 ~) and
a( ~ ~ 0) respectively; the factor e- iKt will be equal to unity for atom I"' and
be -1 for atoms I' and I", as is indicated in Fig. 2.1 by filled, half-filled, and
empty circles. The structure of a real ordered alloy may thus be completely
characterized by the equation
(4.11)
where tn is the translation vector from the initial to the nth atom, and 'f/ is a
parameter that specifies the state at a given (initial) lattice site:
!FA - PBI
'f/= (PA+PB)' (4.12)
with PA and PB the probabilities of the site being filled with species A and B
atoms. These probabilities depend on temperature so that for T ~ Tc 'f/ = O.
For the phase transition described, the quantity 'f/ is an order parameter.
This elementary phase transition in a crystal with one Bravais lattice re-
quires no special group-theoretic analysis.
THE OP FOR ORDERING IN Nb-H AND Ta-H HYDRIDES
Another phase transition type, described by a scalar OP, is the ordering in

interstitial phases. As an example, we examine the hydrides (deuterides)
Nb-H(D) and Ta-H(D) in which, at some temperature, hydrogen is distributed

in an ordered fashion in the tetrahedral interstices and a superstructure forms.
The unit cell of the ordered crystal turns out to be larger than that of the
parent crystal, so the phase transition is specified by a non-zero wave-vector.
The initial lattice of the metal is b.c.c. and the reciprocal lattice that
corresponds to it is f.c.c. Neutron diffraction studies [9] have revealed in the
ordered phase a superstructural (~ ~ 0) type reflection which corresponds to the
occurrence of a new lattice that is described by the wave-vector", = 2;(~ ~ 0).
The superstructural lattice and its unit cell are portrayed in Fig. 2.2.
Fig. 2.2. Relation between the unit cells of the initial phase and those
of the ordered phase for the Nb-H crystal. The dashed straight line
represents the centering vector in the rg cell.
We perform a group-theoretic analysis ofthe ordering of hydrogen atoms in

this crystal and reveal the IR by which the phase transition occurs. Hydrogen
resides in interstices whose coordinates in the primitive cell of the parent metal
having the symmetry group O~ are
1(~ 0 ~), 2(~ ~ 0), 3(0 ~ ~), 4(~ 0 ~), 5(~ ~ 0), 6(0 ~ ~). ( 4.13)
These six points generate one crystallographic position of the space group. Such
positions are pictured in Fig. 2.3, together with other equivalent positions.
The wave-vector of the superstructure belongs to the six-arm star {",9}
and the wave-vector group evidently has 48/6=8 elements in the zero block.
From tables [1], we find that they are constructed from the following point
symmetry elements:
(4.14)
32 CHAPTER 2
Fig. 2.3. Tetrahedral position occupied by hydrogen atoms in the

Nb-H crystal.
which form the space group elements. The latter turn out to have no accom-
panying translations.
We compile a table of permutations of the first atom (interstitial lattice
site) under the action of the group according to the general equation (3.3). For
example, we have for the element {h410}
~1 0)0
o 1
with a41 (h 4 ) = (I 0 0) the returning-translation vector (to save space, we
have represented it as a line). The operations of all group G" elements are
consolidated in Table 2.1. Along with the returning translations, the table also
furnishes the factors 'Yij(g) calculated according to the formula (3.21). Now we
pay attention to the circumstance that under the operation of the G" elements
the atoms 1, 2,4, and 5 transform into each other, whereas the remaining atoms
3 and 6 transform independently. Thus the six-fold position breaks up into two
orbits relative to the group G", viz., a four-fold and a two-fold position. Each
orbit now needs to be considered separately. For the first orbit the stabilizer
Hl of atom 1 consists of two elements, for the second orbit the stabilizer H3 of
atom 3 incorporates four elements:
( 4.15)
Table 2.1
Atomic permutations under the operation of group 0", elements in
Nb-H
h h1 h4 h13 h16 h25 h28 h37 h 40

9
gl 1 4 2 5 4 1 5 2
......
..., II I II I II I I II
;.0 ail (g) 000 100 222 222 101 001 222 222
....
0
Ii! (g) 1 -1 -1 -1 -1 1 -1 -1
g3 3 3 3 3 6 6 6 6
C'I
..., II I 1I I -- 1 II II I
;.0 ai3(g) 000 010 222 222 011 001 222 222
....
0
li3(g) 1 -1 -1 1 -1 1 1 -1
Table 2.2
Irreducible representations of the group of the wave-vector Ii, = ~(11 0)
of the space group O~
h h1 h4 h13 h16 h25 h28 h37 h 40

T
T1 1 1 1 1 1 1 1 1
T2 1 1 1 1 -1 -1 -1 -1
T3 1 -1 1 -1 1 -1 1 -1
T4 1 -1 1 -1 -1 1 -1 1
T5 1 -1 -1 1 1 -1 -1 1
T6 1 -1 -1 1 -1 1 1 -1
T7 1 1 -1 -1 1 1 -1 -1
T8 1 1 -1 -1 -1 -1 1 1
34 CHAPTER 2
Table 2.3
Permutation representation basis functions for Nb-H and Ta-H crys-
tals
i 1 2 4 5 3 6
V
Tl 1 -1 -1 -1
T4 1 -1 1 1
T6 1 1 1 -1
T7 1 1 -1 1
T5 1 -1
T7 1 1
To calculate the basis functions of the permutational representation, we

need to use Table 2.2 of group G" IR [1]. Calculation according to the formula
(4.7) leads to the following results for the orbits 1 and 2:
Thus we have the following constitution of the permutational representation

for the orbits 1 and 2:
1) d; = Tl + T4 + T6 + T7;
(4.16)
2) d; = T5 + T6.
We now calculate the matrix w~v by the formula (4.9). Since, for one-
dimensional representations, the character coincides with the representation
itself, we have, on comparing equations (4.9) and (4.7): w~v = n"v, so that for
the representations contained in d;,
wi v = 1. (4.17)
The components of the basis functions on the other orbit atoms are to be found
from the formula (4.8). For example, according to Tables 2.1 and 2.2, the basis
function components for the representation Tl for the atom 2 pertaining to the
first orbit are
Z= 0 - x
Z=I/4 - A
Z=I/2- 0
z=3/'t -0
(a) (b)
Fig. 2.4. Projection of the crystal structures of the disordered (a) and
ordered (b) phases of the interstitial alloy Ta-H on the (00 1) plane
(D~~ after [11]). Only interstitial sites filled with hydrogen atoms
are shown; the figures correspond to the following heights: +, z =
O·,Ll.,
A Z -- 4' 1. D , z -- 4'.
1. 0 , z -- 2' 3
The calculation results for all the IR's are presented in Table 2.3, which gives
values of the "atomic" components of the basis function at the interstices of
the parent-crystal primitive cell. In the adjacent cells the "atomic" compo-
nents differ in the factor exp( i/d n ), which is equal to -1 for the translations
a( ~ ~ ~), a(±1 00), etc. These data permit one to represent geometrically the
state of an ordered crystal described by basis functions of individual irreducible
representations. In such a portrayal one should bear in mind that all the in-
terstitiallattice sites in the disordered phase at T > Tc are equivalent, and the
probability of their being filled (the occupation probability of these interstices)
is determined by the hydrogen atom concentration C ofthe crystal (the ratio of
the total number of hydrogen atoms to the number of interstices). At T < Tc
these probabilities change and their distribution is characterized by the basis
function. Thus the value of the "atomic" component which is equal to unity
may be treated as an increase of the probability of a given interstitial lattice
site being occupied by hydrogen atoms, and the value equal to -1 denotes a
decrease of the occupation probability. The magnitude of the variation of the
occupation probability is characterized by a temperature-dependent parameter
TJ; it is this parameter which is the OP. The ordering described by the IR 75 of
the star {~g} is characterized by the occupation probabilities of sites 3 and 6;
these probabilities are equal to C + TJ or c - TJ. The corresponding arrangement
36 CHAPTER 2
of the hydrogen atoms in these interstices is depicted in Fig. 2.4. The occupa-
tion probabilities for the other interstitial lattice sites, 1, 2, 4, and 5, remain
equal to C. These structures will conventionally be called "gray" structures.
No "gray" interstices are shown in Fig. 2.4. The symmetry of the ordered
phase that corresponds to the representation T5 of the star {K.9} is described
by the group D~~.
In deciphering the ordered phase structure in the systems Nb-H and Ta-
H, the authors of [11] opted for a "black and white" version: The arrangement
of the atoms at interstices 3 and 6 is the same as that sketched in Fig. 2.4b and
the interstices 1, 2, 4, and 5 are empty. The symmetry of such a structure is
also described by the group D~~. In order to describe such a structure [10], it
is necessary to add to the basis functions T5 of the star {K.9} the basis functions
of the representation T5 of the point r (K. = 0) which are calculated according
to the same scheme.
5. Vector Representation and its Basis
A SUMMARY OF FORMULAS
Our objective now is to consider phase transitions in which the state of each
atom of the crystal in the dissymmetric phase is specified by a polar vector.
Here belong structural phase transitions of the displacive type, transitions to
the ferroelectric phase, etc.
If we assign to each atom in the dissymetric phase some polar vector, then
not only an atomic rearrangement but also a rotation of the atomic vector oc-
curs under parent-crystal space group transformations. The state of the crystal
as a whole should be described by a 30-N-component column vector (with 0-
the number of atoms in a primitive cell) whose individual components indicate
the projection of the vector for each atom. The 30-N -component unit vectors
generate the basis of the vector representation of the crystal space group. Since
a polar vector may be viewed as a tensor of rank one, we may exploit the re-
sults of §3, which are valid for a tensor of any rank. To this end, we need
just to identify the tensor transformation matrix D'f! (g) with the coordinates
transformation matrix R OI f3(g), for the polar vector transforms as the radius
vector (position vector). Thus the matrix of the vector representation d:;' of
the group G,. is determined by the equation
{ dl<m (g)} '01,)1-"

. .,. -- e-i,.Rij(9)o·>,g). R OI f3 (g) , (5.1)
with Q' and f3 running over the three values: x, y, and z (equation (3.7)).
The vector representation evidently coincides with the crystal symmetry

group vibrational representation employed for the group classification of vibra-
tional modes of the crystal, that is, phonons [7]. We will sometimes call the
representation d~ a mechanical representation (hence comes the subscript m
in the symbol d~).
We write out the formulas of the decomposition of the vector representation
in terms of the IR's of the group GI<:
(5.2)
n~ = IIG~II-l LX~(g)XI<V(g), 9 E G~, (5.3)

9
X~(g) = Le-iI<Bjj(9)Oj,gjSpR(g). (5.4)

j
According to the general formula (3.19), the atomic components of the basis
function on the arm", are given by the expression (g E G~)
1jJ" (~V Ii) = L (hr,,](g )e-iI<Bij(9) Oi,gU]R"[I'] ( h), (5.5)

9
and for an arbitrary arm "'L they are expressed in terms of 1jJ"(~Vli) by the
equation
1jJ"GLV li') = e-i"LBili(9L)LR"I'(hL)1jJI'(~Vli). (5.6)
I'
Now we supply the corresponding formulas employed in the stabilizer
method. Instead of the general expressions (3.24), (3.27) and (3.28), we have
for the vector representation
nV = IIH211- 1 L XI<V(h)-Yll(h)SpR(h), (5.7)

h
wiv = 'Yi1(g;) (dI<V(9i) X R(g;))Wj'v, (5.8)
wiv = L(dI<V(h) X R(h)) 'Yll (h). (5.9)

h
The equations written out give two versions of a computational scheme
which permits construction of linear combinations from polar vectors assigned
on parent-crystal atoms transforming according to IR's of the parent-crystal
group. The crystalline structure arising from the initial phase by a displacive
structural transition may be described by a superposition of the basis functions
of a group G" IR that is contained in the mechanical representation. In the
following we consider examples of such description.
38 CHAPTER 2
THE OP AT A STRUCTURAL PHASE TRANSITION IN A-15 COMPOUNDS
We wish to perform a group theoretic analysis of the structural phase transition

in superconducting Nb 3Sn and V 3Si compounds.
Both compounds belong to the same structural type A-15, which has the
space group O~. The lattice is a simple cubic one, with two formula units A3B
per unit cell. At low temperatures that somewhat exceed the superconduct-
ing transition temperature both compounds undergo a phase transition to a
tetragonal phase due to the displacement of species A atoms, as is shown in
Fig. 2.5.
Fig. 2.5. Unit cell of the Nb 3Sn crystal and the displacement of Nb
atoms at a structural phase transition.
The unit cell atoms in the cubic phase of the crystal occupy the positions:
A) 1 (~ ~ 0), 2 (~ ~ 0), 3 (0 ~ ~), 4 (0 ~ ~), 5 (~ 0 ~), 6 (~ 0 ~);

B) 7 (0 0 0), 8 (~ ~ ~).
As can be seen from the figure, at the phase transition the unit cell is
preserved, so the transition is characterized by the wave-vector K, = o. We
demonstrate that the tetragonal phase that arises corresponds to the IR 75
of the group O~. To this end, we calculate the basis functions of this repre-
sentation by invoking the basis of the mechanical representation of the group
GI<=O~.
The group O~ contains forty-eight elements in the zero block:
(5.10)
where the asterisk marks the elements that contain a fractional translation
T = (~ ! !), so that h * = {h IT h}. Under the action of the group O~ elements
Table 2.4
Permutations of the first atom of species A under the operation of the
zero-block elements of the group
hI h2 h3 h4 h5 h6 h7 h8 h9 hlO hll hI2
1 1 2 2 5 6 6 5 3 4 3 4
hi3 hi4 hi5 hi6 hh hi8 hi9 hZD hZI hZ2 hh h24
3 4 3 4 1 1 2 2 5 6 6 5
h25 h26 h27 h28 h29 h3D h3I h32 h33 h34 h35 h36
2 2 1 1 6 5 5 6 4 3 4 3
hh h38 h39 h4D h4I h42 h43 h44 h 45 h46 h 47 h48

4 3 4 3 2 2 1 1 6 5 5 6
(5.10) the atoms of sort A will transform into each other; the permutations of
the first atom are given in Table 2.4. An inspection of this table shows that the
non-zero block of the stabilizer of the first atom is generated by the elements
H:
(5.11)
which constitute the point group C4v . Using the same table the decomposition
of the group O~ with respect to the stabilizer may be represented, for example,
in the form
(5.12)
where the representative elements h3, h6, hs, h g , hID (not involved in the
stabilizer) transform the first atom into all the other species A atoms which
form one orbit:
2 = h31, 3 = h91, 4 = h101, 5 = h81, 6 = h61. (5.13)
We verify that the atomic displacements sketched in Fig. 2.5 are described
by the basis functions of the group O~ two-dimensional IR 75 with K, = O. The
matrices of this representation 75 are written out in Table 2.5. Using the
40 CHAPTER 2
structure of the stabilizer group (equation (5.11)), we can readily calculate the
basis functions of the representation 75. The general formulas (5.7)-(5.9) of
the stabilizer method for the case Ii, = 0 simplify:
nV = 11;011 h~O X"V(h)Sp R(h), (5.14)
wi v = (d"V(g;) x R(g;))W~v, (5.15)
wi v = L (d"V(h) x R(h)). (5.16)

hEHO
For the representation 75 of interest, the formula (5.10) may be written out in
the form
wi = (~ ~) x
V
[R(hd + R(h2) + R(h27) + R(h2S ))
+ C,02 ~) x [R(h17) + R(hlS) + R(h43) + R(h44 )).
The matrices of the point transformations R(h) are written out in tables [1].
Using the tabulated matrices, we obtain the expression
(5.17)
which determines the basis function components on the first atom (we have
omitted the immaterial numerical factor 4). With the help of equations (5.13)
and (5.15) we now obtain the matrices W:,V for the other atoms of the orbit
and represent the result as
v =
'11 12
,
(1 -t) x (1'
-(
0
0
0
D, w;~,= CI ~n ~I X (
0
0
0
D,
W"V
5,6 --
( (2
_(2 ~,) (11 ooo 0)
X
0
0
. (5.18)
Each column of the matrix W:,V determines the two-component set of the basis
function of a given IR. As can be readily shown from the formula (5.14), nV = 1
for 75, so a unique set of basis functions may be constructed in the crystal under
consideration. Taking the first column in the expressions (5.18), we write the
atomic components of the basis functions in the form
Wl,2 = (_~) x (±1 0 0), W3,4 = (_~) x (0 ± 10),
W5,6 = (_:~) x (00 ± 1) (5.19)
(for convenience, we have begun here to represent the non-zero column of the
3 x 3 matrices in the formula (5.18) as a three-component row).
The second set of basis functions
W~,2 = ( _f2)
1 x(±l 00), W;,4 = (-1)
f2 x(O ±1 0), W~,6 = ·(-f)
f x(O 0 ±1)
(5.20)
differs from the first in the common multiplier - f and is therefore linearly
dependent. Thus the expressions (5.19) are the basis functions of the two-
dimensional IR T5 on the vector basis.
The complex character of the basis functions (5.19) is a consequence of
the complex form of the matrices of the IR T5. However, this representation is
real-valued and all its matrices may be brought into real form using the unitary
tr ansformation
d(g) -+
d(g) = Ud(g)U+. (5.21)
As U we choose the matrix
(5.22)
Then all the matrices contained in Table 2.5 are modified into
(~ ~)-+(~ ~), (~ ~)-+( 10 ~1)'

(~ ~) -+ ~ (~ --~), C~ ~) -+ ~ (--Ja -~), (5.23)
(~ f~) -+ ~ (_~ ~), (~ f~) -+ ~ (~ ~).

A calculation with these matrices according to the formulas (5.15) and (5.16)
leads to real-valued basis functions
Wl,2= (v'13) x(±100),W3,4= (-v'3)

1 x(0±10),
(5.24)
W5,6 = (~2) x (0 0 ± 1).
42 CHAPTER 2
Table 2.5
Matrices of the irreducible representation '15 with K, = 0 for the group
O~ [1] (f = exp 2;i)
Elements Matrices Elements Matrices
(~ ~) (~ f~ )
hI, h2, h3, h4, h5, h6, h 7, h8,
h 25 , h 26 , h 27 , h28 h 29 , h 30 , h 31 , h32
h 9 , hIO,hll,hI2,
h 33 , h 34 , h 35 , h36 c; ~) h 13 , h 14 , h 15 , h 16 ,
h37,h38,h39,h40 (~ ~)
(~ f;)
n , h 23 , h 24 ,
C~ ~)
h 17 , h 18 , h 19 , h 2O , h 21 , h
h 41 , h 42 , h 43 , h44 h 45 , h 46 , h 47 , h48
In addition, the calculation results (5.24) for the basis functions may be
represented in tabular form (Table 2.6) by indicating the three-component
vector for each atom. It is now a simple matter to see that the atomic dis-
placements shown in Fig. 2.5 do correspond to the first basis function of the
representation '15.
Table 2.6
Basis functions of the two-dimensional representation '15 of the group
O~ for A-15 crystal
i 1 2 3 4 5 6
1/;
1/;'T': Ii) (V300) (-V300) (0-V30) (0'1'30) (000) (000)
1/;D:( "; Ii) (100) (-100) (010) (0-10) (00-2) (002)

THE OP AT A STRUCTURAL PHASE TRANSITION IN C-15 COMPOUNDS

Similar structural phase transitions occur in some superstructural compounds
with C-15 structure, namely in HfV2 and ZrV 2 [12]. At temperatures well
above Tc they pass from the cubic to the orthorhombic or rhombohedral phase
while preserving the unit cell. Our goal is to identify the possible dissymmetric
°
phases that arise by IR's with", = of the space group Ok of the parent cubic
phase.
The A2B compounds with C-15 structure (Laves phases) have an f.c.c.
lattice with two position types, 16(d) and 8(a), and the primitive cell atoms
have the following coordinates:
A) 1 (~ ~ ~), 2 (~ ~ ~), 3 G~ ~), 4 G~ ~);

B) 5 (0 °0), 6 (t t t)·
This structure coincides with the familiar spinel structure having the general
formula A 2B0 3 , if one removes from it the oxygen atoms located at the cube
vertices, at the center and in the middle of the cube faces.
We calculate the basis functions of the mechanical representation with
'" = 0, making use of the stabilizer method. The group Ok has forty-eight
elements in the zero block, the point elements h13 - h16 being accompanied
by a fractional translation T = (t tt). For the position 16 (d) the atom
1 stabilizer H1 and the representative elements of the decomposition of Ok
relative to fIt are constituted by the following group Ok elements H 1 :
(5.25)
(5.26)
for the position 8 (a) by the elements H5:
(5.27)
(5.28)
The group Ok has ten IR's for", = 0, of which four (71-74) are one-dimensional,
two (75 and 76) two-dimensional and four (77-710) three-dimensional; the rep-
resentations with an even number are odd with respect to an inversion and
conversely. 'Ve have the following constitution of the mechanical representa-
tion on the positions 16 (d) and 8 (a) respectively:
(5.29)
44 CHAPTER 2
We now calculate the basis functions for all the irreducible representations
that constitute the mechanical representation. Using the IR table we obtain,
by virtue of equations (5.15) and (5.16), the following matrix
for the one-dimensional representation T4. The column of this matrix deter-
mines the atomic component of the basis function on the atom 1. We label
this component by 'lj!1. On the other atoms of a given orbit, the basis function
components are determined by the action of the representatives (5.26). Thus
we obtain for the ith atom of the position 16 (d) the polar vector
¢, = (D , ¢, = h,¢, = m' ¢, = h,¢, = (D , = = (D

¢, h,¢,
(5.30)
In their entirety these vectors generate the basis function of the IR T4.
For the three-dimensional representation TS we obtain a 9 x 9 matrix:
0 0 0 0 0 0 0 0 0
0 1 I I 0 1 1 I 0
0 I 1 1 0 I I 1 0
0 I 1 1 0 I I 1 0
\Ii"v
1 -- 0 0 0 0 0 0 0 0 0 (5.31 )
0 1 I I 0 1 1 I 0
0 1 I 1 0 I 1 I 0
0 I 1 I 0 1 I 1 0
0 0 0 0 0 0 0 0 0
which contains the sole line-independent column that determines the atomic
components of the three basis functions on the atom 1. For the other atoms
of the orbit the basis functions are determinable from the formula (5.15) with
the help of equation (5.26). The calculation results for all the IR's involved in
equation (5.29) are summarized in Table 2.7 [13].
As a result of a phage transition by one IR, atomic displacements arise
which may be described by a superposition of the basis functions shown in the
table. A detailed analysis of the resulting structural distortions is carried out

in §9.
Table 2.7
Basis functions of irreducible group representations with K, = 0 on the
vector basis (u = 2 - va,
v = 1- va)
i 1 2 3 4 5 6
7
74 111 III III III

uIi! u1v uIv u1i!
76
lUi! Iuv 1uv lUi!
011 011 oIl 011

78 101 101 101 101
lID lIo 110 110
100 100 100 100 100 100
710 010 010 010 010 010 010

001 001 001 001 001 001
011 oIl 011 011
7{0 101 101 101 101

110 110 110 lID
100 100
77 010 010
001 001
6. Pseudovector Representation and its Basis
A DESCRIPTION OF THE MAGNETICALLY ORDERED STATE

The transition from the paramagnetic to the magnetically ordered state in
the crystal is characterized by the occurrence of a mean magnetic moment
46 CHAPTER 2
vector on the atoms. The state of a magnetically ordered crystal as a whole

may be specified by a 30-' N -component vector column (0-' is the number of
magnetic atoms in a primitive cell of the parent crystal), each component of
which indicates the projection of the atomic magnetic moment. It stands to
reason that such a vector column describes the state of a magnetic crystal only
with neglect of the possible crystal lattice distortions accompanying the spatial
ordering of magnetic moments.
Under the action of the parent-crystal space group elements this multi-
dimensional vector will transform with allowance for the fact that the atomic
magnetic moment vector transforms as a pseudovector. The 30-' N -component
unit vectors in this space generate a basis of the pseudovector representation of
the space-group. The matrices of this representation with a given wave-vector K,
may be obtained from the general expression (3.7) for the tensor representation
by identifying the matrix D'l! (g) with the matrix by which the pseudovector
transforms:
D'l!(g) -> 8g RcxfJ(g) (a,j3 = x,y,z). (6.1)
Here 8g = 1 if the rotational part h of the space group element 9 =
{hITh}
is a first-order operation (pure rotations), and 8g = -1 if h is a second-order
operation (inversion, reflection, inverse rotation). The matrix RcxfJ(g) is the
coordinate-transformation matrix. The pseudovector representation will often
be referred to as the magnetic representation and labelled by the symbol dXl.
The magnetic representation is reducible:
dM = Ln'Md"v. (6.2)
v
The multiplicity factor n'M of the group G" IR may be calculated according
to the formulas (5.3) and (5.4) of the preceding section, subject only to the
correction that the matrix RcxfJ (g) should be replaced by 8g RcxfJ (g). Introducing
the same correction, the formulas (5.5)-(5.9) for calculating the basis functions
of the pseudovector representation become valid too.
A magnetic structure that is specified by a given wave-vector may be
represented as a superposition of pseudovector basis functions of some IR d"v
of the wave-vector group [14] of the initial (paramagnetic) phase of the crystal.
It would, however, be not out of place here to note that the symmetry group of
a paramagnetic crystal (what is known as the paramagnetic group Gl') is not
quite identical to the crystal space group but is a direct product of the group
G by the spin inversion group R:
Gl' = G x R, (6.3)
(the latter consists of two elements, R = 1, I'). All the irreducible representa-
tions of the group G multiply into a doubled set of even and odd group G1'
IR's with respect to I'. It may be shown that the group G1' magnetic represen-
tation does not incorporate even representations at all and that the magnetic
structure is described only by odd representations of the paramagnetic group.
The formula for calculating the basis functions of odd group G1' representa-
tions coincides with that for the corresponding group G basis functions. For
this reason the magnetic phase transition from the paramagnetic state of the
crystal may be described by the pseudovector basis functions of the IR's of the
space group G [15].
THE OP AT A MAGNETIC PHASE TRANSITION IN A GARNET
We provide a group-theoretic description of the magnetic structure of the garnet

(Mn3A12Si3012). A detailed analysis of all the known magnetic structures
of garnets is given in [14]. \Ve consider the chosen garnet with a view to
illustrating the method for calculating the basis functions of the pseudovector
representation and to refer these to the magnetic structure observed.
The garnets have a b.c.c. lattice and space group O~o. In the garnet under
consideration, the magnetic Mn atoms occupy the positions 24 (c), the twelve
atoms in the primitive cell of the crystal having the coordinates:
1 (~ 0 t), 2 (t ~ 0), 3 (0 t ~), 4 (~ 0 ~), 5 (~ ~ 0), 6 (0 ~ ~),
7 (~ 0 t), 8 (t ~ 0), 9 (0 t ~), 10 (~ 0 ~), 11 (~ ~ 0), 12 (0 ~ ~).

The magnetic structure corresponds to Ii, = 0 and the magnetic moments
of the twelve atoms specified are oriented as follows:
(provided that 2V = U). Thus the magnetic moments form a triangular mag-
netic structure and lie in planes perpendicular to the body diagonals of a cube
(Fig. 2.6).
It is known that this magnetic structure is described by the 3-dimensional
IR 710 (n = 0) of the group O~o. We calculate the basis functions of this
representation on the pseudovector basis. The stabilizer of the atom 1 contains
48/12=4 elements H:
(6.5)
48 CHAPTER 2
Fig. 2.6. Projection of the magnetic structure ofthe garnet Mn3AhSi3012

on the (1 1 1) plane
As representatives of the decomposition of the group OJ.° relative to H, we may

choose the following elements OJ.°:
h5 h3 h10 h31 h33

(6.6)
3 4 5 9 11
beneath which we have written the numbers of the atoms that are obtained
from the atom 1 by the action of a corresponding representative.
vVe write out the matrices of the representation T10 of the requisite group
OJ.° zero-block elements:
h1 h2 h17 h 1S h3
no no n
0 0 0 0 0
G DG 1
0
I
0
0
I
0
1 DO 1
0
h5 h7 h9 hlO h25
n
1 I 0 0 0
G DO DG DO
0
0
0
0
0
1
0
I DO I
0
The calculation of the basis functions is carried out according to the for-
mulas (5.7)-(5.9), with allowance for the fact that the matrix R(h) should be
replaced by 15 h R(h). Using the formula (5.7), we find for '110 the number nV = 3;
thus we should obtain three sets of basis functions that transform according
to this representation. The quantity W~v calculated according to the formula
(5.9) should be a 9 X 9 matrix. We represent this matrix in block form (the
numbering of the blocks corresponds to the numbers of the IR basis functions):
A= ( 02 00 0)
0 ,
0
B= ( 0
0 0)
1 0 ,
0 0 0)
D= ( 0 0 1 . (6.7)
o 0 0 o 0 1 010
This matrix determines the atomic components of the basis functions on the
atom 1. For the atoms 2 and 3, for example, the quantity W~v calculated
according to the formula (5.9) has the following structure:
W2v = hgW~V
0
= ( A'
D'
0 ~')
B"
D" B"
DII) ,
o B' D' o o
(6.8)
where A', B', D' are obtained by premultiplying the matrices A, B, D into
15 hg R( h g ), and A", B", D" into 15h. R( h s ). The same applies to the other atoms.
The non-zero columns of the matrices Wfv give the atomic components of the
basis functions. Inasmuch as the representation '110 is involved in the magnetic
representation three times, we have three independent columns. We take the
non-zero columns, viz., the first, the fifth, and the sixth. We label their total-
ity for the ith atom by "pi; then, employing the expressions (6.7) and (6.8), we
50 CHAPTER 2
obtain for the first triplet (set of three orbital atoms):
2 0 0 0 1 0 0 1 0
0 0 0 0 0 0 0 0 1
0 0 0 0 0 1 0 0 0
0 0 0 0 0 0 0 0 1
\[11= 0 1 0 \[12 = 2 0 0 \[13 = 0 1 0 (6.9)
0 0 1 0 0 0 0 0 0
0 0 0 0 0 1 0 0 0
0 0 1 0 0 0 0 0 0
0 1 0 0 1 0 2 0 0
Proceeding in similar fashion, we calculate '!f!i for the nine atoms of the orbit
that remain. The final result may be represented in the form of Table 2.8.
Table 2.8
Pseudovector basis functions of the representation TlO for a garnet
crystal with magnetic atoms in position 24( c) ('" = 0)
T T10 T{O Til

10
i ,,\=1,,\=2..\=3 ..\=1..\=2..\=3 ,,\=1,,\=2 "\=3
1 100 - - - 010 001 - 001 010
2 - 010 - 100 - 001 001 - 100
3 - - 001 100 010 - 010 100 -

4,5,6 + + -
7,8,9 - - +
10,11,12 - - -
The atomic components of the basis functions are written out in explicit form
only on the first trio of atoms. On the next following trios, the atomic com-
ponents are obtained by multiplying the above components into +1 or -1, as
shown at the bottom of the table
It is clear now that the magnetic structure written as relations (6.4) is

obtained by combining the basis functions TlO and TIo with equal mixing coef-
ficients
TlO(C C C) + T{O(C' C' C'), (6.10)
subject to the condition that C = -2C'.
References

and Breach (1965).
2. C.W. Curtis, and A. Reiner: Representation Theory of Finite Groups and
Associated Algebras, Wiley (1982).
3. V.K. Zakharov: Kristallografiya 23,918 (1978).
4. O.V. Gurin, and V.Yu. Irkhin: Fiz. Met. Metal/oved. 54, 1051 (1982).
5. Yu.A. Izyumov, and O.V. Gurin: J. Mag. Magnet. Mat. 36, 226 (1983).
6. G.Y. Lyubarski: Application of Group Theory in Physics, Pergamon (1980).
7. A.A. Maradudin, and S.H. Vosko: Rev. Mod. Phys. 140, 1 (1968).
8. J .L. Birman: 'Theory of Crystal Space Groups and Infra-red and Raman
Lattice Processes of Insulating Crystals', in S. Fliigge (ed.), Handbuch der
Physik 25/26, Springer (1974).
9. Yu.Z. Nozik, R.P. Ozerov, and K. Hennig: Strukturnaya Neitronografiya
(Structural Neutronography), Atomizdat (1981).
10. O.V. Gurin, V.E. Naish, and V.N. Syromyatnikov: Fiz. Met. Metalloved.
57, 215 (1984).
11. V.A. Somenkov, V.F. Petrunin, S.Sh. Shilshtein, and A.A. Chertkov:
Kristallografiya 14, 617 (1969).
12. S.V. Vonsovsky, Yu.A. Izyumov, and E.Z. Kurmaev: Superconductivity of
Transition M eials, their Alloys and Compounds, Springer Series in Solid-
State Sciences 27, Springer-Verlag (1982).
13. Yu.A. Izyumov, V.E. Naish, and V.N. Syromyatnikov: Kristallografiya 21,
256 (1976).
(Neutron Diffraction of Magnetics), Atomizdat (1981).
15. Yu.A. Izyumov,and V.E. Naish, J. Magn. Magnet. Mat. 12, 239 (1979).
CHAPTER 3
Symmetry Change at Phase Transitions
7. Change in Translational Symmetry
THE BRILLOUIN ZONE AND THE SYMMETRIC POINTS IN IT
Spontaneous crystal symmetry lowering at a phase transition occurs both as a

result of a decrease in the number of rotational symmetry elements and as a
result of the reduction of some translations. This reduction gives rise to a new
lattice type which in the general case occurs in the thinned-out translation
network of the initial phase and characterizes the dissymmetric phase. The
problem of the full symmetry change may be solved in two stages, by consid-
ering first the changes in translational symmetry only. In purely theoretical
terms, the problem consists in enumerating all the lattice types that may be
obtained from a given lattice as a result of some phase transition and ascertain-
ing how these dissymmetric-phase lattices are imbedded into the initial-phase
lattice. When viewed in an experimental aspect, the problem resides in finding
the dissymmetric-phase lattice with the help of a structure investigation by
X-ray structure analysis, neutron diffraction, etc. Comparing the lattices of
the dissymmetric and the initial phase enables one to identify the wavevector
star that specifies the irreducible representation according to which the phase
transition occurs.
The purpose of this section is to establish a relation between the wave-
vector star and the dissymmetric-phase lattice. Before outlining the formula-
tion of this problem, it would be helpful to recall the major concepts of the
direct and reciprocal crystal lattices.
Each crystal lattice is unambiguously prescribed by three shortest trans-
lations, t 1 , t 2 , and t3' For the crystal lattice symmetry to be reflected most
fully, one introduces the concept of the Bravais cell, the shape of which should
correspond to the crystal point symmetry. In choosing a Bravais cell, one tries
52
SYMMETRY CHANGE AT PHASE TRANSITIONS 53
to ensure that the number of right angles is at a maximum and the cell vol-
ume is minimal. Along with the Bravais cell, one also exploits the concept of
the primitive cell, which is constructed on the three shortest crystal transla-
tions t l , t 2, t3' As an example, Fig. 3.1 illustrates the relation between the
primitive cell and the Bravais lattice for f.c.c. crystals.
4Z
a,O-----~:J
Fig. 3.1. The primitive cell and Bravais cell of the f.c.c. lattice.
Using equations (2.1), one can construct for each Bravais cell a correspond-
ing reciprocal-space cell, called a Wigner-Seitz cell. Its edges are generated by
the reciprocal-lattice primitive translation vectors b l , b 2 , b 3 • However, it is
the concept of the Brillouin zone that has proved to be the most convenient
for physical applications. The procedure of constructing a Brillouin zone boils
down to the following steps. Connect the chosen reciprocal lattice site with
the nearest sites. Through the middles of these segments, pass planes that
are perpendicular to them. If these planes generate a convex polyhedron, we
obtain the Brillouin zone. Otherwise we connect the chosen reciprocal lattice
site with the next nearest sites and, again, draw through the middles of the
resulting segments perpendicular planes with respect to the latter.
It is evident that the final result, that is, the shape of the Brillouin zone,
depends ultimately on the ratios of the Bravais lattice parameters. Thus, for
example, the Brillouin zone shape for a rhombohedral lattice depends on the
ratio of the Bravais cell height c to the base edge length a. For the case ~ > ~
the Brillouin zone is sketched in Fig. 3.2,a, and for ~ < ~ in Fig. 3.2,b. For
other lattices, a similar description of the Brillouin zones is available in books
[1,2].
Using the symmetry of the reciprocal lattice, it is possible to classify all the
points that belong to a Brillouin zone. A specific role in solid state physics is
54 CHAPTER 3
Fig. 3.2. Brillouin zones for the rhombohedral lattice for ~ > ~ (a)
and ~ <~ (b); r(O 0 0), F(O 0 ~), T(~ ~ 0), L(~ ~ ~).
played by what is called the symmetric or Lifschitz points. These are Brillouin
zone points that have a specific high symmetry, that is, some set of symmetry
elements that leave a given point fixed or transform it into an equivalent one.
A feature peculiar to the Lifschitz points is that the representation of the
appropriate vector", in terms of the vectors hI, h 2 , h3 contains numerically
fixed coordinates, whereas for the non-Lifschitz points it contains some running
parameters. In addition to the symmetric points, it is customary to single out in
the Brillouin zone symmetric lines and planes. Figures 3.2 through 3.5 present
the symmetric points for the lattices r rh, r c, r~, and r{.
A complete list of Lifschitz points for all Brillouin zones is given in Ta-
ble 3.1. The first column of the table indicates the symbol of these points
according to [1]. The second column gives the symbol of the wave-vector star
corresponding to a particular point after Kovalev [3J. The third column spec-
ifies the coordinates of a point in the reference frame of the reciprocal lattice
Bravais cell (in units of 2:). The fourth column gives the notation of the star
Fig. 3.3. Brillouin zone for the simple cubic lattice r c; reo 0 0), X (0 ~ 0),
MO ~ O),R(~ ~ ~).
Fig. 3.4. Brillouin zone for the f.c.c. lattice r{; reo 0 0), W(l 0 ~),
L(~ ~ ~), X(O lO).
arms in terms of the primitive translation vectors of the reciprocal lattice. The
last column furnishes the representative elements whose operation on the first
star arms permits the remaining arms to be obtained.
Now we are in a position to perform a straightforward analysis of the
changes in the translational symmetry of a crystal at a phase transition over
56 CHAPTER 3
Fig. 3.5. Brillouin zone for the b.c.c. lattice r~; reo 0 0), H(O 1 0),
P(~ ~ ~), N(~ ~ 0).
Lifschitz stars. This problem was first solved by Lifschitz in his celebrated
paper [4]. In what follows we present an approach that enables one to obtain
the change of the lattices in the case of a magnetic phase transition as well [5].
ARM MIXING AND THE TRANSITION CHANNEL
In analyzing the translational properties of a phase that arises as a result of

a transition according to the parent-crystal space group IR DI<V, it suffices to
consider an expansion of the dissymmetric-phase density function in the form
p(t n ) = L eil<Ltn PL(O), (7.1)

L
where the summation over L is performed over all the arms Kl, K2, ... of the
star {K}. This equation relates the density in the nth crystal cell to the density
LL PL(O) in the zero cell from which the nth cell is separated by the translation
vector tn of the initial phase. The equation of interest may be derived from
the general density expansion (1.19), assuming the phase transition to go over
one star and allowing for the fact that the IR basis functions for the star arms
contain the factor exp(iKLt n ).
The quantity PL(O) should be called the arm contribution to the density
function. This quantity contains information about the density distribution in
the zero cell, but the details of this distribution as well as the symmetry of
Table 3.l.
List of Lifschitz points for all Brillouin Zones
Designation: (1) symmetric point, (2) star number, (3) coordinates of
arm ~l at reference point Bi, (4) star arms, (5) representatives of k 4 .
1 2 3 4 5
Lattice f tr ; = B l , b 2 = B 2, b 3 = B3
bl
222 ki = !(bi + b 2 + b 3) hl
1 1 I
R 1
2 22 ki = !(b2 + b 3)
all hl
U 3 2 12 ki = !(bi + b 3)
10 hl
V 4 110
22 kl = !(bl + b 2) hI
X 5 100
2 kl = !b l hl
6 0102 kl = !b2 hl
Z 7 00 12 kl = !b3 hI
Lattice f m ; b l = B I , b 2 = B 2, b 3 = B3
D 8 2 2 kl = !(bi + b 3)
101 hI
C 9 22 ki = !(b2 + b 3 )
all hI
222 kl = !(b 1 + b 2 + b 3) hI
I I I
E 10
Z 11 00 12 kl = !b3 hI
B 12 100
2 kl = ~bl hl
Y 13 010
2 ki = ~b2 hl
A 14 110
22 ki = ~(bl + b 2) hI
58 CHAPTER 3
Table 3.1 continued
1 2 3 4 5
Lattice rb .
m' bl = HBl - B 3), b 2 = B 2, b 3 = HBl + B3)
V 4 2 2 kl = ~b2' k2 = -~b3
101 hlh4
222 kl = ~(bl + b 2), k2 = -~(bl + b 3) hlh4

1 1 1
L 5
A 7 0 120 kl = ~bl hl
Y 8 100 kl = Hb2 + b 3) hl
M 9 1102 kl = Hb 1 + b 2 + b 3) hl
Lattice ro; b l = B l , b 2 = B 2, b 3 = B3
X 20 100
2 kl = ~bl hl
Y 21 0 120 kl = ~b2 hl
Z 22 00 12 kl = ~b3 hl
T 23 22 kl = ~(b2 + b 3)
0 11 hl
U 24 2 2 kl = ~(bl + b 3)
101 hl
S 25 110
22 kl = ~(bl + b 2) hl
222 kl = ~(bl + b 2 + b 3)
1 1 1
R 26 hl
Lattice rb.
0, b l = ~(Bl + B2), b 2 = ~(Bl - B2), b 3 = B3
S 12 110
22 kl = ~bl' k2 = -~b2 hlh2
222 kl = ~(bl + b 3), k2 = -Hb2 + b3) hlh2

1 1 1
R 13
Y 15 010 kl = ~(bl + b 2) hl
z 16 00 12 kl = ~b3 hl
T 17 0112 kl = ~(bl + b 2 + b 3) hl
Table 3.1 continued
1 2 3 4 5
Lattice rl; b 1 = ~(-B1 +B2 + B3), b 2 = ~(B1-B2+B3)' b 3 = HB1 +B 2-B3)
1 11
L 10 222 kl = Hbl +b2+b3),k2 = -~b3,k3 = -tb2,k4 = -~b1 h1h2h3 h4
-222 kl = ~b1,k2 = -~(b1+b2+b3),k3 = ~b3,k4 = ~b2
1 1 1
L 11 h1h2h3h4
2-22 kl = ~b2,k2 = ~b3,k3 = -Hbl +b2 + b 3),k4 = ~b1 hlh2 h3h4
1 1 1
L 12
1 1 1
L 13 22-2 kl = ~b3,k2 = ~b2,k3 = ~b1,k4 = -~(b1+b2+b3) h1h2h3h4
T 15 100
2 k1 = ~(b2+b3) h1
Y 16 0120 kl = ~(bl +b3) hl
Z 17 00 12 kl = ~(b1 +b2) h1
Lattice ra; b 1 = HB2+B3), b 2 = ~(B1 +B3), b 3 = ~(B1 +B 2)
10 22 k1 = Hb2+b3), k2 = ~(b1-b3)
111 hlh4
11 2 2 kl = ~(bl +b3), k2 = ~(b1-b2)
111 h1h4
12 H1
22 kl = ~(bl +b2), k2 = ~(b3-b1) hlh4
S 13 22 kl = ~bl' k2 = ~(b2-b3)
011 h1h4
R 14 2 2 k1 = ~b2' k2 = ~(b1-b3)
101 hIh4
T 15 110
22 kl = ~b3' k2 = ~(b2-bl) h1h2
222 k1 = i-(b1+b2+b3), k2 = -k1

W 16 11 1 h1h25
X 18 111 k1 = ~(b1 +b2+b3) hl
Lattice r q; b l = B 1, b 2 = B 2, b 3 = B3
X 15 0120 kl = ~b2' k2 = -~b1 h1h13
M 16 011
22 k1 = ~(b2+b3), k2 = -~(b1 +b3) h l h l3
R 18 110
22 ki = ~(bl +b2) h1
S 19 00 12 kl = ~b3 h1
A 20 1 1 1
222 k1 = ~(b1 +b 2 +b3) h1
60 CHAPTER 3
Table 3.1 continued
1 2 3 4 5
Lattice r~; b 1 = HB 2+B3), b 2 = ~(Bl +B3), b 3 = HBI +B 2)

2 2 kl = ~b2,k2 = ~bl,k3 = ~(b3-bl),k4 = Hb3-b2) hlh14h2h16
N 11 101
1 1 1
P 12 222 kl = :t(b 1 +b2+b3), k2 = -kl hlh25
22 kl = ~b3' k2 = Hb 1 -b2)
X 13 110 hlh14
M 15 001 kl = !(b 1 +b2-b3) hI
Lattice rc; b 1 = B 1 , b 2 = B 2, b 3 = B3
X 10 00 12 kl = ~b3' k2 = ~b2' k3 = ~bl hl h5h 9
22 kl = ~(bl +b2), k2 = ~(bl +b3), k3 = ~(b2+b3)

M 11 110 hl h 5h 9
1 1 1
R 13 222 kl = ~(bl +b2+b3) hI
Lattice r{; b 1 = ~(-Bl +B2+B3), b 2 = ~(BI-B2+B3)' b 3 = ~(BdB2-B3)
W 8 10 12 kl = ~(bl +b2)+~(b2+b3)' k2 = -kl hlh25
k3 = :t(b 1 +b3)+~(bl +b2), k4 = -k3 h5 h 29
k5 = :t(b2+b3)+~(bl +b3), k6 = -k5 h g h 33
L 9 2221 1 1
kl = ~(bdb2+b3),k2 = ~bl,k3 = ~b2,k4 = !b3 hlh26 h 27h28
X 10 001 kl = ~(bl +b2), k2 = ~(bl +b3), k3 = ~(b2+b3) hl h 5h 9
Lattice r~; b 1 = HB 2+B3), b 2 = HBI +B3), b 3 = ~(Bl +B 2)
N 9 11022 kl = ~b3,k2 = ~b2,k3 = ~bl,k4 = !(b2-bI) hl h5h9h 2
k5 = !(b3-bI), k6 = Hb3-b2) h6 h U
p 10 1 1 1 kl = :t(b 1 +b2+b3), k2 = -kl hlh25
222
H 12 001 kl = ~(bl +b 2-b3) hI
Table 3.1 continued
1 2 3 4 5
Lattice r rh; b 1 = Bb b 2 = B 2, b 3 = B3
F 4 OOl2 kl = ~b3' k2 = ~b2' k3 = ~bl hl h3h5
T 5 EO
22 kl = Hb 1 +b2), k2 = ~(bl +b3), k3 = Hb2+b3) hlh3 h5
1 1 1
L 8 222 kl = ~(bl +b2+b3) hl
Lattice rh; b 1 = B 1 , b 2 = B 2, b 3 = B3
M 12 loa
2 kl = ~bl' k2 = ~b2' k3 =-~(bl+b2) hlh3 h5
J( 13 EO
33 kl = Hb 1 +b 2), k2 = -kl h 1h 13
L 14 lOl
2 2 kl = Hb 1 +b3), k2 = Hb2+b3), k3 = -Hb 1 +b2-b3) hlh3 h5
1 1 1
H 15 332 kl = ~(bl +b2)+~b3, k2 = -kl h 1h 13
A 17 OOl2 kl = ~b3 hl
PL(O) turn out to be immaterial in addressing the problem of the translational

properties of the dissymmetric phase. However, the lattice type, as an impor-
tant characteristic of the translational properties of this phase, substantially
depends only on which of the arm contributions PL (0) are non-zero. The total-
ity of vectors "'L of the entire star for which the arm contributions are different
from zero, will be called a transition channel [6]. According to which of the
arms participate in the channel, one obtains a particular type of lattice, which
is char acterized by a system of translations t D. The vectors t D are determined
from the requirement that the density function p(t n ) be invariant under all
translations of the new phase.
Using the expression (7.1) one obtains the equations
(7.2)
which should be written only for the arms "'L involved in the transition channel.
The solutions of these equations may, broadly speaking, be different for the
various versions of arm mixing, and this points to the necessity of introducing
the concept of the transition channel.
62 CHAPTER 3
Rather than solving the system of equations (7.2), it is convenient in prac-

tice to try (for a given transition channel) the various parent-lattice translations
tn and to pick out those that satisfy these equations. From the small num-
ber of vectors tn thus picked out, one can readily ascertain the vectors of the
shortest translations tD and determine the new lattice type. Such work should
be carried out for all the transition channels over the Lifschitz stars, since it
is only for the Lifschitz stars that a new-phase lattice can be obtained which
is commensurate with the parent lattice. In the case of non-Lifschitz stars
the factors exp(i~Ltn) depend on a continuous parameter (or several parame-
ters) that determines the magnitude of wave-vectors of the same symmetry, so
that the new phase does not, generally speaking, correspond to a space group.
And it is only at some "fortuitous" values of the running parameter that the
commensurate periodicity of the new phase occurs.
The transitions over non-Lifschitz stars will be described in Chap.9; mean-
while here we illustrate the role of the transition channel via the example of
phase transitions from the b.c.c. lattice over a six-arm Lifschitz star {~9} with
the arms (Table 3.1):
The shortest vectors of the direct and reciprocal crystal lattices in the rectan-
gular coordinate system have the form
2~ 2~ 2~
b1 = -(0
a
1 1), b2 = -(1
a
0 1), b3 = -(1
a
1 0), (7.5)
the being the primitive translation vectors of the Bravais cell (cube edges).
ai
To start with, we consider the transition over the arm ~l (one-arm chan-
nel). The unique equation exp(i~ltD) = 1 is satisfied for
(7.6)
The first three vectors are the shortest translations of the lattice rg imbedded
into the parent rc lattice, as sketched in Fig. 3.6a. The transition over another
arm, for example ~2, gives the system of translations
(7.7)
(b)
Fig. 3.6. r~ lattices arising from the r~ lattice in the one-arm channels
of the star {~g}.
Thus the same rg lattice arises which is inserted into the initial-phase lattice in
a different fashion (Fig. 3.6b). Each of the six arms of the star (7.3) evidently
describes the same lattice, which is oriented in one of the six ways relative to
the parent lattice.
Consider now the two-arm channels. In the channel (~1~4) the system of
equations
(7.8)
is satisfied by the vectors
which generate the lattice r q. A lattice of the same type, but imbedded in
a different way, arises in the channels (~2~5) and (~3~6). However, in the
two-arm channel (~4~5) we obtain a lattice r rh which is determined by the
vectors
(7.10)
The same lattice obtains in all the remaining two-arm channels, etc.
The results of a similar investigation of all the possible Lifschitz stars for
all the fourteen initial Bravais lattices are summarized in Table 3.2 [6]. The first
column indicates the symbol of the lattice resulting from a phase transition over
a given channel. The second column gives three Bravais cell edges, expressed
64 CHAPTER 3
in terms of the parent-lattice Bravais cell edges al, a2 and a3' In the case of
centered lattices the semicolon is followed by a specification of the centering
translations. The third column gives the change in primitive cell volume at
the transition. In the next two columns the corresponding transition channel
is indicated: The fourth column gives the number of the star according to
Kovalev (Table 3.1) and the total number of star arms (in parentheses), while
the fifth column specifies the set of arms participating in the transition. The
following notation is adopted here: (i) denotes that any star arm participates
in the transition, (ij) stands for any pair of arms taking part in the transition,
etc.; the parenthesized numbers (12), (34), (123), etc., indicate exactly which
arms participate in the transition.
This table lists all the possible changes of the lattices at a transition over
Lifschitz stars. Such results were first obtained by Lifschitz [4] and later repro-
duced in a book [7]; however, the above writings did not specify the transition
channels.
Table 3.2.
Lattices liable to arise as a result of a translation over Lifschitz stars
for 14 Bravais lattices
Transition Channel
f fD Description of the Bravais cell
of the new lattice n star star arms
1 2 3 4 5 6
ftr f tr 2al, a2, a3 2 1-7
fm fm 2al, a2,a3 2 12-14
fm al, a2, 2a3 2 11

fbm 2al, 2a2, a3; al + a2 2 8-10
fbm fbm al,a2,2a3;~(al +a2) 2 7,9
fm al,a2,a3 2 8
ftr al + a2, ~(al - a2), a3 2 4(2),5(2) (i)

fbm 2al, 2a2, a3; al + a2 4 4(2),5(2) (12)
Table 3.2 continued
r:n
~
~
1 2 3 4 5 6 ~
M
~
ro ro 2al,aZ,a3 2 20-22
~
rb0 2al, 2az, a3; al + az 2 23-25 C1
::Il
:>
rf0 2al,2az,2a3;aZ + a3,a3 + al,al + az 2 26 Z
Q
M
rg rb0 al, az, 2a3; ~(al + az) 2 16
~
ro al,aZ,a3 2 15 '"C
::Il
1( . :>
r:n
rg al,aZ, 2a3;"2 al + az + a3) 2 17
M
~
rm a3,al +az, ~(al- az) 2 12(2) (i)
~
2al,2~, Hal +az);al +~ 2 13(2) (i) Z
rbm r:n
~
rg 2al, 2az,~; al + az 4 12(2) (12) oZ
rf0 2al,2az,2a3;al + a3,a3 + aZ,al + az 4 13(2) (12) r:n
rf0 rg al,aZ,a3; Hal + az) 2 15-17
rtr ~(al + az), ~(al + a3),aZ + a3 2 10-13(4) (i)

L-- 0)
Ct
0>
0>
Table 3.2 continued
1 2 3 4 5 6
.
rbm 2al, 2az, 2"1 ( al + a3); al + az 4 10-13(4) (ij)
rf0 2al,2aZ, 2a3;aZ + a3,a3 + al,al + az 8 10-13(4) (ij k), (1234)
rg ro al,az,as 2 18
rbm as,al + aZ,al - az; Hal + az + a3) 2 10(2)-15(2) (i)
C1
rb0 2al, 2az, a3; al + az 4 10(2)-15(2) (12) ::I:i
;..-
'i:i
rf0 2al,2az,2a3;aZ + a3,a3 + al,al + az 4 16(2) (i), (12) ~
tr1
2 19 ::::0
rq rq ab a Z, 2a3 ~
rq al +az,al -az,as 2 18
rvq al + az, al - az, 2a3; al + a3 2 20
ro 2al,aZ,a3 2 15(2) (i)

rg 2al,2a3,aZ;al +a3 2 16(2) (i)
rq 2al,2aZ,a3 4 15(2) (12)
rvq 2al, 2az, 2a3; al + az + a3 4 16(2) (12)
-. _ .. '--.- ----
Table 3.2 continued
en
-<
~
1 2 3 4 5 6 ~
trl
2 15 1-3
rvq rq al,a2,a3
~
rl>0 al + a2, a3, al - a2; ~(al + a2 + a3) 2 13(2) (i) C1
=
>
rl>m al,a2 + a3,a2 - a3; ~(al + a2 + a3) 2 11(4) (i) Z
o
trl
rq al +a2,al-a2,a3 4 13(2) (12)
~
r~ 2al,2a3,a2;al + a3 4 11(4) (13), (24) '"C
=
>
en
rl>m 2a3,2(al - a2), Hal + a2 + a3);al - a2 + as 4 11(4) (12),(14),(23),(34)
trl
1-3
rvq al + a2, al - a2, 2a3; al + a3 4 12(2) (i), (12)
~
2at, 2a2, 2a3; al + a2 + a3 8 11(4) (ijk), (1234) Z
en
rvq
......
1-3
rc rq al,a2, 2a3 2 10(3) (i) oZ
en
rq al +a2,al -a2,a3 2 11(3) (i)
r{ 2al, 2a2, 2a3;a2 + a3,a3 + al, al + a2 2 13
rq 2al,2a2,a3 4 10(3) (ij)

0>
-:j
0>
ry:,
Table 3.2 continued
1 2 3 4 5 6
rvc 2al,2az,2as;al +az +as 4 11(3) (ij), (123)
rc 2al, 2az, 2a3 8 10(3) (123)
rvc rc al,aZ,a3 2 12
o
r0b al, az + as, az - a3; Hal + az + a3) 2 9(6) (i) :::r:1
>
"'0
rq al + aZ,al - aZ,a3 4 9(6) (14), (25), (36) I-j
trl
i=C
rrh al - ~(-al + az + a3),aZ - Hal - az + a3),a3 - Hal + az - a3) 4 9(6) (ij) except (14), (25), (36), C,..)
(126), (135), (234), (456)

rfc 2al, 2az, 2a3;aZ +a3,a3 + al,al + az 4 10(2) (i), (12)
rvc 2al,2az,2a3;al +az +as 8 9(6) (ijk) except (126), (135),
(234), (456);
(ijkl), (ijklm), (123456)
L--l.....--- --_.-
Table 3.2 continued
en
-<
~
1 2 3 4 5 6 ~
trl
~
rfc rq Hal +az),Ha l-az),a3 2 10(3) (i)
~
(i) (1
rrh al + !(az + a3),az + Hal + a3),a3 + Hal +az) 2 9(4) ::x::
rc al,aZ,a3 4 10(3) (ij), (123) z>-
Q
trl
rg 2al,aZ +as, Haz - a3);al + Haz + as) 4 9(4) (ij)
~
rvq al,aZ,2a3;a3+ !(al +az) 4 8(6) (i), (12), (34), (56) '"0
::x::
r{ 2al, 2az, 2a3;aZ + a3,a3 + al,al + az 8 9(4) (ijk), (1234)
>-
en
trl
~
rq 2al,2aZ,a3 16 8(6) (1234),(1256),(3456)
~
(123), (124), (125), (126), Z
en
::3
(134), (156), (234), (256), (3
z
en
(345), (356), (456), (13),
(14),(15),(16),(23),(24),
(25),(26),(35),(36),(45),(46) 0)
~
-1
o
Table 3.2 continued
1 2 3 4 5 6
rc 2al,2az,2as 32 8(6) (135), (136), (145),

(146), (235), (236),
(245), (246), (ijkl) except
Q
(1234), (1256), (3456), ::r::
>-
'i:i
(ijklm), (123456) ~
tr:l
~
rrh rrh az + as, as + al, al + az 2 8 c:...o
rmb al +az,al-az, 2as;al 2 4(3) (i)
rm al + aZ,al - az,as 2 5(3) (i)

rbm 2(al + az), 2(al - az), as; 2al 4 4(3) (ij)
rrh -al + az + as, al - az + as, al + az - as 4 5(3) (ij), (123)

rrh 2al, 2az, 2as 8 4(3) (123)
Table 3.2 continued
en
>-<
~
1 2 3 4 5 6 ~
M
~
fh fh at,aZ, 2a3 2 17
~
fo at + aZ,at - aZ,a3 2 12(3) (i) Q
=
>
fV0 at + az, at - az, 2a3;at + az 2 14(3) (i) Z
o
M
fh at + 2az, at - az, a3 3 13(2) (i), (12)
~
fh fh 2at,2az,a3 4 12(3) (ij),(123) '"d
ff0 2(at +az), 2(at-az), 2a3; 2at,at +aZ+a3,at-a Z+a3 4 14(3) (ij)
=
>
en
M
~
fh at + 2aZ,al - az, 2as 6 15(2) (i), (12)
~
fh 2at, 2az, 2a3 8 14(3) (123) Z
--_._.-
en
~
(3
Z
en
-'I
......
72 CHAPTER 3
MAGNETIC LATTICES
The foregoing analysis of the lattice symmetry change may be extended to

include magnetic phase transitions giving rise to magnetic structures that are
described by the Shubnikov symmetry. What serves as the initial phase is the
paramagnetic phase of the crystal. The paramagnetic phase is described by the
paramagnetic group of symmetry G1' which includes, along with all the space
group elements g, also the elements gl', where I' is the spin reversal operation.
As a result of a phase transition, a magnetic structure may arise which has as
the symmetry group the Shubnikov group M. The latter is always a subgroup
of the group G1' and it is for this reason that the magnetic phase transitions
may be incorporated into the symmetry-approach scheme.
In the general case the magnetic groups contain, in addition to the ordinary
translations by the vector t, also so-called anti translations, that is, combined
elements from an ordinary translation and from the element I'. We label the
translations and antitranslations of a magnetic crystal by tD and tD respec-
tively. The spin density of such a crystal should be described by the expression
(7.1). Allowing for the invariance of this expression under all translations tD
and for the reversal of sign for all anti translations t D, we obtain the equations
(7.11)
for determining all the vectors tD and tD for a given transition channel.
Consider, as an example, the magnetic phase transition from the f.c.c.
lattice over the three-arm star {,dO} with the arms (Table 3.1):
(7.12)
b i being the primitive translation vectors of the reciprocal b.c.c. lattice:

211" - 211" - 211" -
b 1 = -(111), b 2 = -(111), b 3 = -(111). (7.13)
a a a
By solving the basic equations (7.11), we find the translations and antitrans-
lations that generate the Bravais cell of a magnetically ordered phase for each
transition channel. Thus at the transition over one arm K.l
(7.14)
(7.15)
/!1
rmJm
jrJ(j-_____--<J
Pc 4/rnrnm PmJrn
Fig. 3.7. Magnetic lattices arising from the r~ lattice by one, two and
three arms of the star {,dO}. Dark and clear circlets represent sites
connected by antitranslations; the asterisks mark parent-lattice sites
that are not related to black-and-white sites by either translations or
antitranslations. These parent-lattice sites will sometimes be called
'lost' translations.
and over three arms ~1, ~2, ~3
(7.16)
The resulting magnetic lattices are displayed in Fig. 3.7.

Such analysis, performed in [8] for all the fourteen Bravais lattices, lll-
dicates that one of the thirty-six Shubnikov-symmetry magnetic lattices may
arise as a result of a phase transition over one of the Lifschitz star channels.
A complete table of magnetic lattices arising in all transition channels of all
Lifschitz stars is presented in [5]. That table as well as Table 3.1 exhaustively
solves the problem of the change in the translational symmetry of the crystal
at phase transitions over Lifschitz stars. Phase transitions over non-Lifschitz
stars will be treated in Chap. 9.
74 CHAPTER 3
8. The Total Symmetry Change
PRINCIPLES FOR FINDING THE SYMMETRY GROUP

OF A NEW PHASE
We have investigated a change in part of the crystal symmetry at a phase

transition, a change that is due to translational properties of the crystal. The
total symmetry change includes a decrease in the number of initial-phase group
G rotational elements and is wholly characterized by the symmetry group G 1
of the final phase that occurs as a result of a phase transition. The search for
the possible groups G 1 should be made on the basis of four criteria.
1) The symmetry group of the new phase should be a subgroup of the
symmetry group of the initial phase:
G1 C G. (8.1)
2) The group 01 is an admissible group of the new phase (at the transition
over the representation DII of the initial-phase group G) if the restriction of
this representation to the aforementioned group contains the identity represen-
tation.
This criterion, due to Birman [9], follows from the fact that the density
function p of the new phase should be invariant under the subgroup G 1 , and an
invariant is a quantity that transforms according to the identity representation.
Therefore, being reducible in the general case, the restriction of the group G
IR to the subgroup G 1 should contain the identity representation. Otherwise
the group G 1 cannot arise by the irreducible representation DII.
3) If the suspected groups of the new phase turn out to involve two sub-
groups, G1 and Gi, so that one of them is a subgroup of the other (for example,
Gi C Gd and, in addition, both are admissible according to the Birman crite-
rion and are obtained at a transition over the same representation, then only
the maximal group (G 1 in this case) should be left in the final list of subgroups.
This maximal-subgroup principle follows from the natural requirement that the
description of the crystal symmetry be complete: It is necessary to enumerate
in the group all the symmetry elements that are available in the crystal after
the phase transition.
4) The representation over which the phase transition goes should be part
of the corresponding tensor representation (permutational, mechanical, mag-
netic, etc.) realized on the parent crystal. This reflects the real structure and
physical content of the order parameter.
The requirements enumerated above substantially restrict the list of ad-

missible subgroups (criteria 1 and 3) and admissible IR's (criteria 2 and 4).
It stands to reason that relevant experimental data on the structure of the
dissymmetric phase should be employed here. From a structural investigation
one normally knows the wave-vector of this structure; from a knowledge of
the wave-vector it is then possible to determine the wave-vector star as the
characteristic of the IR.
Selecting subgroups according to the criteria 1-4 and choosing IR's does
not solve the problem as to the character of the phase transition described. To
ascertain whether a second-order phase transition is possible, one needs to find
out if the responsible IR is active. This is done by using the Landau criterion
(1.25).
The symmetry analysis of the phase transition presupposes primarily solv-
ing one of the two problems: Given a group G of the initial phase of the crystal
and given a wave-vector star {K}, determine the list of possible symmetry
groups G 1 of the new phase or from the symmetry groups G and G 1 of the
initial and final phases respectively, determine the IR according to which the
phase transition G ...... G 1 has occurred. Both problems can be solved by purely
group-theoretic methods, without invoking the thermodynamic potential mini-
mization procedure. Since, in doing so, we do not pose the problem concerning
the character of the phase transition (what is essential is only that it should be-
long to the class of continuous phase transitions), we do not include the Landau
criterion (1.25) of an active or passive representation among the enumerated
criteria. If the kind of the phase transition is known from experiment, we need
additionally to explore the activity of the admissible IR.
The information about the relation of the groups G 1 to the IR may be
further extended by using the Landau expansion of the density function p as
a series in the IR basis functions. Assuming the phase transition to occur
according to only one IR of the group G, we represent p as
p= I:CA<PA' (8.2)
A
where <PA is a basis function of the space-group IR D{I<}v and A is a combined

subscript A = (L, A), with L the number of the wave-vector star arm and A the
number of the wave-vector group basis function.
As the symmetry group G leaves the dissymmetric phase invariant, the
following equation holds for each element (g E G 1):
T(g)p=p. (8.3)
76 CHAPTER 3
Using equations (8.2) and (2.9), we rearrange the left-hand side of equation
(8.3) to read
T(g)p = L CXT(g)tPA = L CX L Di~lv (g)tPAI =

A A A'
Substitution of this expression in equation (8.3) yields the equation
CX = L Di1,v(g)CX"
A'
(8.4)
which relates the mixing coefficients to the matrices of the IR D{"}v.

If we are given a group Gl and if we have determined (from the Birman
criterion) the IR D{"}v according to which the phase transition G -+ G 1 occurs,
the equation (8.4) determines the constraints, imposed by the symmetry of
the phase, between the mixing coefficients. To determine all the relations, it
suffices to consider only group Gl generators. As a result, we obtain some
specialized set of mixing coefficients {Cr, C!J, ... , Crv} for which the symmetry
of the density function p is described by the group G 1 .
An inverse statement of the problem is also possible: Given a specialized
set of mixing coefficients, find the group G. To this end, it is necessary to
write equations (8.4) for each element 9 of the initial group G 1 and to pick out
those elements that turn the equations into identities. A complete set of such
elements constitutes the symmetry grou p G 1 of a given phase. The values of the
coefficients CX evidently play no role here; it is only their relative values that
count. Therefore, the symmetry of the phase is determined only by the type of
mixing coefficients, and to determine the possible groups G 1 corresponding to
a given IR, it suffices to enumerate all the mixing coefficient types possible. For
a two-dimensional representation, for example, they will be four in number:
{C,O}, {C C}, {C e}, {C1 C 2 }, (8.5)

for a three-dimensional representation there will be nine types:
{C OO}, {C CO}, {C eo}, {C1 C 2 0}, {C C C},

{C C e}, {C C Cd, {C e Cd, {C1 C 2 C3 } (8.6)
etc. The symbol {C1 C 2 }, for example, denotes that C 1 and C2 are different
(but C 1 :/; ±C2 ).
For three-dimensional representations we certainly should obtain, for ex-

ample along with the specialized set {e 0 O}, two more sets, {O e O} and
{O 0 e}, which apparently describe a phase of the same symmetry but cor-
respond to a different imbedding of the group G 1 into its subgroup G. The
totality of all such equivalent sets will be denoted by (e 0 0). All the possible
mixing coefficient types for a given representation are determinable automat-
ically if we make an exhaustive search for all the subgroups G 1 of the group
G that are admissible according to the Birman criterion at a phase transition
over a given representation. Thus a complete group-theoretic characteristic
of the dissymmetric phase is the specification of its symmetry group, of the
responsible IR, and of the type of mixing coefficients.
Details of the above-described group-theoretic scheme for analyzing a phase
transition can be well illustrated by an example.
AN EXAMPLE OF A GROUP-THEORETIC METHOD OF SEARCHING FOR

DISSYMMETRIC PHASES
In §5 we have already performed some analysis of structural phase transitions

observed in a number of A-15 and C-15 compounds. That investigation was
aimed at calculating (for the IR's responsible for the phase transition from the
initial cubic phase of the crystal) the basis functions in terms of which the
atomic displacements occurring at a temperature below the structural trans-
formation temperature are expressed. It is our intention now to explain in
what fashion the responsible IR's were determined from the space groups of
the aforementioned crystals that had undergone phase transformations. Let
us state the problem more broadly: For both structures, namely, A-15 (space
group O~) and C-15 (space group oD, we need to determine the list of all
the admissible (as a result of a phase transition with", = 0) subgroups and to
indicate for each of them the irreducible representation by which a subgroup
may arise [10].
To begin with, we should have a list of all the subgroups for the groups O~
and Oh that correspond to the preservation of the primitive cell of the crystal.
A convenient reference manual on these subgroups is one by the authors of [11].
For each space group [11] indicates only the independent subgroups maximally
rich in recurring elements, whereas the other may be written out by descending
stepwise from the "maximal subgroups" to the trivially small subgroup c~. The
term "maximal subgroup" will henceforth be applied only with reference to
maximal rotational symmetry, for cell-non-preserving transitions will not be
treated.
78 CHAPTER 3
Table 3.3
Selection of the group of the new phase according to the Birman
criterion
Crystal Subgroups Subgroups Subgroups admissible

system according to Birman
A15 C15 B2 Oh Ag Au Bg Bu Eg Eu F2g F2u F 1g Flu

02 04 01 0 ++
Cubic
T4 T2d T1
d d Td + +
T1h T4h T1h Th + +
T1 T2 T1 T ++ + +
D~h D!~ D!h D4h + +
D~d D~d D~d DZ'x + + + +
2d
D~d Dn D~d DZ'x y + + +

2d
Tetra- CJv ClJ Clv C 4v + + +

gonal D~ Dlo Dl D4 ++ + +
Clh cgh Cl h C 4h + + +
C~ cg Cl C4 ++ + + + +
8 41 8 42 8 41 84 + + + + + +
D~d D~d D~d D3d + +
D~ D~ D~ D3 ++ + +
Rhombo- cgv C~v C~v C 3v + + + +
hedral
C§i C§i C§; C3i + + + +
Cj Cj Cj C3 ++ + + + + + +
Table 3.3 (continued)
Crystal Subgroups Subgroups Subgroups admissible

system according to Birman
0 3h 0 h7 Oh Ag Au Bg Bu Eg Eu F 2g F 2u F lg Flu
D§h
D24
2h
DZ'x
2h + + +
DZ'x y
20
D 2h D28
2h 2h + + +
Dl
2
D7
2
DZ'x
2 ++ + + + +
D6
2
D9
2
DZ'XY
2 ++ + + + +
Ortho-
C 13
2v
C 20
2v
Cz,x y
2v + + + + + +
rhombic C1 6 Cxy,z
2v
22
C 2v 2v + + + + +
Civ 19
C2v cz,x
2v + + + + +
Ch C~h qh + + + + +
qh Cih
xy
C2h + + + + +
Ci C~ C2 ++ + + + + + + + +
Mono- C~ Ci C2xy ++ + + + + + +
clinic
Csl Cs4 C sZ + + + + + + +
CS4 C83 cxy
8 -I- + + + + + + +
Tri-
C~, C~
• Ci + + + + +
clinic
ct C1l Cl ++ + + + + + + + +
80 CHAPTER 3
The left-hand half of Table 3.3 gives all the cell-preserving subgroups for
the space groups O~ and oX of the structures A-15 and C-15. The number of
these subgroups is the same in both groups and is equal to thirty-two. This is so
because the point group Oh has thirty-two subgroups with crystallographic ally
non-equivalent orientations. Each of the subgroups will have a space subgroup
of its own. Thus the lists of the thirty-two space subgroups for the structures
A-15 and C-15 differ only in the upper numbers of these subgroups. As the
general notation of these subgroups straightforwardly for all the structures, we
may take, for the time being, the notations of the corresponding point class
from column 4. Similar point subgroups with different orientation in the class
Oh differ in Table 3.3 in the orientation indices of their generators: In the
International Notation
zx - z xy - zx
D 2d = 4z 2x m xy , D 2d = 4z2xymx, D 2" = mzmxmy ,
D;"x y = mzmxymxy, c~~xy = 2zmxymxy, ....
The subgroups are grouped into blocks according to crystal systems. The
right-hand half of Table 3.3 enumerates the admissible subgroups according
to Birman for all the IR's of class Oh; these subgroups are marked with a +
symbol.
Using this table, it would be easy to write a list of admissible (maximal)
subgroups obtained from each IR. To this end, one needs to take only those
IR's that are involved in the mechanical representation. For the structure A-15
(the structural formula of the compound is A3B) this representation has the
following constitution (calculated according to the formula (5.1)):
(8.7)
and for the structure C-15 (the structural formula of the compound is A2 B)
(8.8)
As a further step, we need to determine the type of mixing for each admis-
sible IR that leads to the symmetry of the phase described by a given group G1 .
We wish to illustrate this stage of work by a particular example. We choose
the three-dimensional representation TS for the structure C-15. In Table 3.3
there are in this case twelve subgroups G 1 that are admissible according to Bir-
man. We take the first of them, Dn. The density function of the new phase is
P = Po + Dp, where
(8.9)
should be invariant under the group G 1 = Dn. We separate from the group
Oh IR 78 matrices the restriction of the representation to the subgroup D~dxy.
Requiring that 6p be invariant under D~dxy, it suffices to take only the gener-
ators of this group: h38(4zI) and h16(2xy). Acting with the representation 78
matrices of these elements on the vector column of the mixing coefficients, we
obtain a system of equations,
G~1 D(;,) G:)

-1
o
o
from which it follows that C 1 = C 2 = 0; the coefficient C 3 may be arbitrary.
Thus the group D~dxy corresponds to the {O 0 C} type of mixing coefficients.
Eliminating the crystallographic equivalence, which is unimportant to us, we
will simply write (0 0 C). Analogously, this procedure may be performed for
all the twelve admissible subgroups G 1 . The results are as follows: For the
groups Dn, 51, D~, CJ;, C~ we obtain similar sets (00 C), for the groups
D~, Ci the set (C C ±C), for the group C§ the set (C1 C 2 0), and, finally, for
the group ct the set (C1 C 2 C 3 ). Having a table of subgroup relations among
the space groups [11], we single out the maximal subgroups according to each
mode mixing type. For the five types of mode mixing we obtain
(00 C) - Dn, (C C ± C) - D~, (C ± CO) - ciJ,
(8.10)
The summarizing Table 3.4 specifies the maximal groups G 1 of the new
phase according to each type of mode mixing for all the IR's (there is no mixing
of modes for one-dimensional representations and the table gives simply the
maximal groups for a given representation). All the groups G 1 are given in the
notation of the point groups in order that Table 3.4 may be suitable for both
structures A-15 and C-15 at once. When examining a particular structure one
should replace these notations by the symbols of the space groups, using the
left-hand half of Table 3.3. The representations 71 and 72 are not contained in
Table 3.4 since they are not involved in the mechanical representation for any
one of the structures.
For a final discussion of the results, it is necessary to abridge the resulting
list of groups with the help of experimental data on the crystal system of the
new phase. The final results for the structures A-15 and C-15 respectively will
be:
D9 D 2d'
A- 15 ·. ~h' 5 C4,,,
7 C4h'
2 .
(8.11)
C-15: D~~, ciJ, D~ or D~d' D~, C~v.
82 CHAPTER 3
Table 3.4
Groups of the new phase and mode mixing types for all IR's in A-15
and C-15 compounds
73 74 Mode mixing type 75 76 Mode mixing type 1"7 78 79 710
C C
C, (2 ± v'3)C 00 C D Z,xv D Z,xv C
D4h D4 2h 2d 4h C4v
ThTd CCO - C~:'z C;K C~:'Z
C C
C, -(2 ± v'3)C - DZ'X

2d CCC D3d D3 C3• C3v
C cCl cxy c~y - cxy
2h s
- - C 1C 20 - C•Z - C 8z
C1 C2 D~;'x D~'x C 1 C2C3 Ci C1 Ci C1
The wavy line indicates the groups arising from the passive representations in
which the phase transition is of first order. It is this situation that occurs in the
N aCl-structure compounds V 3Si and Nb 3Si where the tetragonal-phase space
group corresponding to the two-dimensional IR 75 of the group O~ turns out
to be D~h.
9. Domains
DOMAINS AS A CONSEQUENCE OF THE CURIE PRINCIPLE
Most of the phase transitions come about when the temperature is varied; as a
rule, the crystal symmetry reduces as the temperature is lowered. In keeping
with the Curie principle (which states that the dissymmetry which has arisen in
the system should be present also in the causes that generate it), the symmetry
of the crystal should not change when the temperature is varied, for the effect
of temperature on the crystal has the symmetry of a scalar. The paradox noted
is resolved as follows. At a phase transition crystals break up into domains.
The symmetry of each domain is lower than the parent-crystal symmetry, but
the arrangement of the domains in the crystal is determined by the symmetry

elements lost at the transition, in consequence of which the crystal symmetry
as a whole remains unchanged in conformity with the Curie principle.
But if a single-domain state occurs in the crystal at the phase transition,
then, in a sufficiently large totality of identical crystals, all domains will be
represented to an equal degree, so that on the average the symmetry of such
an assembly remains unaltered. Actually, however, the causes for the break-up
of crystals into domains are of an energetic character. Owing to the fact that
some energy is spent to form domain walls, the free energy of a polydomain
crystal may turn out to be lower than that of a single-domain crystal.
In what follows we restrict ourselves to group-theoretic aspects of describ-
ing the crystal domain structure.
A SYMMETRY CLASSIFICATION OF DOMAINS

A great contribution to the exploration of the symmetry problem of domain
structures in ferroelectrics has been made by Zheludev, Shuvalov [13,14]' Aizu
[15,16], Ascher [17], J anovec [18], and other researchers. The results obtained
by these authors are reflected in papers [19,20] dealing with the symmetry
classification of domains in crystals. This classification is general in character
irrespective of the nature of the order parameter and is determined only by the
transformation properties of the latter under the operation of the initial-phase
symmetry elements.
Consider a symmetry-non-preserving phase transition C -+ CD. As a
result of the lowering of the symmetry, the new phase is characterized by a set
of spontaneous quantities that form the OP components TJA. A complete set
of such quantities will be labelled by the symbol 'l}a = {TJA}, where Ct numbers
the various orientations of the dissymmetric phase relative to the initial phase.
Allowing for its particular imbedding in the parent group, we denote the group
of the dissymmetric phase by CD.
From the definition of the order parameter, it follows that the group CD
is a maximal subgroup of the parent group C that leaves the parameter 'l}a
invariant (see also §8). Thus CD is a stabilizer 'l}a in the group C. The group
C may be decomposed into cosets relative to the stabilizer CD:
C = gfC D + g'2C D + ... + g;:C D , (9.1)
where g'{ is the identity element and the representative elements g$ of the
decomposition (9.1) transform the vector TJa into an equivalent vector TJ(3:
'I}(3 = g$'I}a. (9.2)
84 CHAPTER 3
The set of vectors 11" obtained by the action of the representatives of the de-
compost ion (9.1) on 110/ forms an orbit of 110/ relative to the group G. Since
there corresponds to each equivalent vector 11" some domain of the dissymmet-
ric phase, the number of different domains n is equal to the number of cosets
in the decomposition (9.1):
_ II Gil (9.3)
n-IIGDII'
IIGII and IIGDII being the orders of the groups G and GD respectively.
The stabilizers of different vectors 11" are evidently conjugate groups:
G"D = g"O/GO/D (g"0/) -1 ,g"0/ E G . (9.4)
It may happen that some of the representatives g/1 do not change the group GD.
Such a set of elements, including the elements of the group G D itself, forms a
group and is said to be the normalizer NG D of the group GD in the group G.
In this case the domains corresponding to the elements of the normalizer NG D
have a common symmetry group GD. The number of such domains d is equal
to the number of cosets in the decomposition of the normalizer N G D relative
to the subgroup GD:
NG D = GD+gfGD+ ... +llGD· (9.5)
Thus the number of different domains n may be expressed as
n= md, (9.6)
m being the number of different subgroups GD in the group G. The number m

is also equal to the number of cosets in the decomposition of G relative to the
normalizer NG D. The number d indicates the degeneracy of the dissymmetric
phase. The phase G D is considered to be non-degenerate (d = 1) in the case
when the normalizer NG D coincides with the group G D itself.
The equations (9.1)-(9.3) given here constitute the basis of the symmetry
classification of domains (the last equations (9.4)-(9.6) only refine it). The
classification rests on the symmetry of the initial and final phases. However,
as we have seen, each low-symmetry phase may be unambiguously described
by the number of the irreducible representation and by a particular set of
basis-function mixing coefficients. Put another way, each dissymmetric phase
may be unambiguously associated with some vector 'fJ in the multidimensional
space of the order parameter (see §14). The stabilizer ID of this vector is a
subgroup of the abstract point I-group, that is, a subgroup of the "image" of
the responsible IR. A classification of domains may be constructed also within
the framework of the relation between the I and ID groups that act in the OP
space. The number of domains will then be equal to the number of cosets in
the decomposition of the I group relative to the subgroup ID or equal to the
ratio of the orders of these groups
(9.7)
Both approaches, based on interrelations of the space groups G and G D
and the abstract groups I and ID, are completely equivalent; so are the corre-
sponding methods of constructing invariant expansions of the thermodynamic
potential.
ARM, ORIENTATIONAL AND ANTIPHASE DOMAINS
The introduction of the concept of the transition channel (§7) has made natural
the introduction of a more detailed physical classification of domains. The
expression (9.3) for the number of domains, equal to the index of the subgroup
G D in the group G, may be rearranged to read
(9.8)
GO, G~ being the corresponding point groups of the phases and T, TD their
translation groups. The numbers no and t respectively indicate the factor by
which the number of rotational and translational elements decreases.
We wish to see what constitutes the first cofactor 1]0 in the expression
(9.8). Let the phase transition be accompanied by an increase in unit cell
volume, that is, let the transition go over a non-zero wave-vector star {"'}. In
an overwhelming majority of the phase transitions observed, the transition goes
over a one-arm channel of the star. The symmetry group of the dissymmetric
phase at this transition either coincides with the wave-vector group, GD = G",
or a subgroup of it, GD c G". In the first case the number of domains differing
in orientation coincides with the number of arms (no = I,,). We call such
domains arm domains. In the second case an additional domain structure may
arise within each arm domain with a fixed arm "'L. Such domains are said to
be rotational. The number of rotational domains is easy to determine from the
equation
IIG~II
m = IIG~II" (9.9)
86 CHAPTER 3
The totality of arm and rotational domains will be referred to as orientational

domains. The number of such domains is
no = mlk. (9.10)
In addition to orientational domains, the occurrence of what is known as

translational or antiphase domains is possible. These domains may be obtained
by the action of initial-phase translations, non-preserved at a given transition,
on the first domain. The number of translational (antiphase) domains is deter-
mined by the second cofactor t in the expression (9.8). All symmetry-allowed
domains may be obtained from a given domain by using the representative
elements of the decomposition of the group G relative to the subgroup G" and
using the decomposition of G" relative to its subgroup GD. It stands to rea-
son that this holds true only for dissymmetric phases obtained via a one-arm
channel. Cases of many-arm channels call for a separate treatment.
Thus we write out the decomposition of the initial group G into cosets of
the wave-vector group G,,:
I"
G= LgLG", (9.11)
L=l
where gL = {hLIThL} and hL is a representative of the arm "'L =gL"'l. The
expression (9.11) completely defines the number of and the type of domains for
GD = G". If GD C G", then we need to decompose the group G" into cosets
relative to the subgroup
m t
G" = LgrGD + LgsGD. (9.12)
r=l s=l
Here gr stands for representatives of rot.ational domains in the zero block, and
9 s = {h1Its} for the 'lost' translations of the group G". If we now decompose
the group G with respect to the subgroup G",
(9.13)
we will readily see that the representative element of an arbitrary domain is

either the element ga = gLgr (for purely orientational domains) or ga =
gLgs
(for translational domains).
The decomposition (9.13) enables all the other domains to be obtained
from a particular domain. Let the first domain (dissymmetric phase with wave-
vector "') be specified by the vector quantities uJ prescribed on the parent-

crystal primitive-cell atoms. In the rth rotational domain (with a fixed arm "')
the set of atomic vectors uj should be determined from the equation
(9.14)
where gr is a representative in the decomposition (9.12) ofthe group G" relative

to the group G D, R(gr) is the rotation matrix corresponding to this element,
and the atomic numbers i and j are related by the operation of the element
gr on the ith atom: gr(jO) -+ (ia;j). This relation follows from the general
definition (3.5) of the action of a symmetry element on the unit vector of the
multidimensional vector space.
In a translational domain of the number s the atomic vectors are related
to the vectors specifying the first domain by the evident equation
(9.15)
Finally, the relation of the atomic vectors in two arm domains (the Lth and
the first) is given by
(9.16)
which follows from equation (3.32).
EXAMPLES OF AN ANALYSIS OF THE DOMAIN STRUCTURE
1. Find the number and type of domains that are liable to arise at a struc-
tural phase transition O~ -+ D~h in A-15 compounds (§5). This transition
occurs without changes in translational symmetry ('" = 0) and therefore no
arm domains arise.
We choose as the symmetry group of the first domain the group D~h(Z),
where Z denotes the orientation of a four-fold axis. Then the coset decom-
position of the initial-phase symmetry group O~ relative to D~h(z) has the
form
(9.17)
where g5 = {h510} and g9 = {h910} are, according to [3], rotations about

three-fold axes. The structure of the first domain, sketched in Fig. 3.8a, is
described by the mode mixing type (C 0) of the two-dimensional representation
75. Atomic displacements in the second and third domains are obtained under
the operation of the elements g5 and g9 on the first domain. These domains
88 CHAPTER 3
Fig. 3.8. Three rotational domains in V3Si and Nb 3Sn (A-15

structure).
are depicted in Figs. 3.8a and 3.8b (the calculations have been carried out
according to formula (9.14)).
2. Find the number and type of domains in C-15 compounds undergoing
=
a structural phase transition from Ok with K- O. In the compounds HN 2 and
ZrV 2 the symmetry of the low-symmetry phase has not yet been determined
unambiguously. A knowledge of the domain structure may prove to be essential
for a conclusive solution of this issue. According to the experimental data
available, the dissymetric phase has either the symmetry D5~ or D~d [10]. As a
result of the Ok -+ D~d transition four types of domains should arise, as there
are four representative elements of the decomposition of the group Ok relative
to D~d : gl, g6, g7, gs· As can be seen from Table 3.4, the group D~d may be
obtained as a result of a transition over the three-dimensional representation
7S with the mixing coefficients (C C C). To obtain the structure of the rth
domain, we act on the structure of the first domain with the elements g6, g7,
and gs. The results of calculations according to the formula (9.14) are cited in
Table 3.5 and sketched symbolically in Fig. 3.9 (to make the figure simpler, all
the cell atoms are reduced to a point).
For the structural phase transition Ok -+ D5~ we may choose gl, g2, g5,
g6, gg, gll as the representative elements. The atomic displacements in the first
domain are described, according to §5, by the representation 7S(0 0 C). The
other five domains are obtained by the action of the representative elements on
the first domain. The results of this operation are consolidated in Table 3.6.
3. Consider now the domain structure that arises at a transition with
K- =F O. As has been shown in §4, the ordering of hydrogen atoms in the
Ta-H(D) and Nb-H(D) systems is described by one star {K-9} arm of the parent
disordered phase group O~. The symmetry of the ordered phase (see Fig. 2.4)
{ 5
Fig. 3.9. Domain structure in A2B (C-15) compounds arising at the

transition Ok -+ D~d with Ii, = O. The arrows indicate atomic dis-
placements. The number of an arrow denotes the number of an atom
undergoing a given displacement. The double arrows refer to displace-
ments of species B atoms, the single arrows refer to displacements of
species A atoms.
is described by the group G D = D~g. In this example we thus deal with the
case G~ = G~ = D2h and G D C G,., that is, only arm and antiphase domains
should arise. As the elements of the decomposition of the group O~ relative
=
to G" D~~ we may take the representative elements of the arms li,L =
gLIi,l
which are given in Table 3.1, namely, gl, g2, g5, g6, g9, gu. The group
G" = D~~ may in turn be decomposed into two cosets relative to the subgroup
G D = D~~ with Ii, f:. 0:
(9.18)
where gs = {h1Its}, and one of the lost translations of the initial phase is
ts = a3, a1 + a3, a2 + a3 (Fig. 2.4). As a result, twelve domains should arise at
the transition (Fig. 3.10); each of the domains may be obtained from the first
90 CHAPTER 3
domain by the action of the elements gl, gIg., g2, g2g8, g5, g5g., g6, g6g.,
g9, g9g$, gll,gllg.·
Table 3.5
Domain structure in C-15 compounds at the phase transition
oX -+ D~d with", = O.
Domains Atoms A Atoms B
1 2 3 4 5 6
l(gl) 000 all 101 110 111 III

2(g6) all 000 IIo 101 III III
3(g7) 101 110 000 all III III
4(g8)
-
110 101
-
all 000 III 111
Table 3.6
Domain structure in C-15 compounds at the phase transition
oX -+ D5~ with", = o.
Domains Atoms A Atoms B
1 2 3 4 5 6
l(gI) 110 IIo 110 110 001 001

2(g2) 110 110 110 IIo 001 001
3(g5) 101 101 101 101 010 010
--
4(g6) all all all all 100 100
5(g9) 101 101 101 101 010 010
6(911) all all all oIl 100 100
Btl BB
.:.
[J [J
4 ....
[J a
I [J
L[Jgggs
z ==
t [J
II It
Igg
-0
z f /2 -6
Z == J/4 -x
z 1 -0
z = J/2 - ....
Fig. 3.10. Domain structure in the interstitial phases ofTaH and NbH
at the phase transition O~ - D~~ over the star {K9}. Projections of
the unit cell of ordered phases on the z = a plane.
OZ . Az-1.xz-3·Oz-1· A Z _3
, -_ l4'~' - 2' , - 4' , - ,~, - 2
10. The Paraphase
THE INITIAL PHASE AND THE PARAPHASE
Both symmetric and thermodynamic methods of describing the subgroup-

memory phase transitions treated in the monograph are based on the expression
(1.19) for the crystal density function, which is represented as a superposition of
group G IR basis functions. The entire body of information about the evolution
of the crystal is therefore contained in the characteristics of the high-symmetry
phase G, generally referred to as the initial phase.
An overwhelming majority of phase transitions in crystals proceed in such
a fashion that as the temperature is lowered the high-symmetry phase suc-
92 CHAPTER 3
ceeds a low-symmetry phase at some value of Te. Hence there naturally follows
the generally accepted initial-phase selection principle according to which one
should choose as the initial phase the high-temperature phase, the most sym-
metric of the phases really observed. Thus it is normally the paramagnetic
phase of the crystal that serves as the initial phase for magnetic phase transi-
tions.
In a number of cases, however, such an approach to the selection of the
initial phase does not allow the entire set of observed properties to be described
correctly. Thus in some crystals a domain structure is liable to occur in the
high-symmetry phase G existing up to the melting temperature. Such a do-
main structure is characterized by the following properties. First, the various
domains may be brought into coincidence with each other by crystallographic
symmetry elements that do not belong to the group G observed. Second, by
applying external fields, a displacement of domain boundaries and a change-
over of domains can be observed. The presence of a domain structure with
these properties below the melting point may be viewed as the result of a
hypothetical phase transition Go --+ G, with Go a hypothetical initial phase.
For example, the occurrence in an orthorhombic crystal of domains that are
transformed into each other by a hexad axis C6 is indicative of a hexagonal
hypothetical initial phase.
The concept of a hypothetical initial phase may prove constructive also
m another situation. In some crystals undergoing a G --+ G 1 transition it
is not possible to correctly describe the entire set of observed characteristics
(susceptibility, the temperature dependence of the order parameter, the type
of the phase diagram, etc.) proceeding from the type of the thermodynamic
potential <1> constructed for the relevant representation DV of the group G.
Assuming that a hypothetical Go --+ G --+ G 1 transition may exist, another
potential <1>0, invariant for the group Go, may be constructed that provides an
adequate description of the phenomena observed.
Finally, crystals exist that exhibit G 1 --+ G 2 phase transitions where
the groups G 1 and G2 are not symmetrically related, that is, G 1 (j. G 2 and
G 2 (j. G 1 . In these crystals the atomic displacements u at such transitions
satisfy the condition u ~ a, where a is the lattice spacing. Such transitions
may, nevertheless, be described using Landau's phase transition theory if one
introduces a hypothetical initial phase Go such that Gl C G2 and G2 C Go
and if one considers the sequence of transitions Go --+ G 1 --+ G 2 •
In all the cases where specific characteristics of a crystal undergoing a phase
transition cannot be described correctly on the basis of the high-temperature

initial phase G actually observed, it may therefore be assumed that a hypothet-
ical phase, not realized for some reasons or other, whose symmetry group Go
is a supergroup of the group G observed, is present for these crystals and the
potential <1>0, invariant under the group Go, correctly describes the observed
anomalies in the physical properties of the crystal in the vicinity of the phase
transition. Such a hypothetical phase will henceforth be called a paraphase.
The concept of the paraphase was introduced into Soviet literature by
Levanyuk and Sannikov in 1971 [21] when describing a sequence of transitions
in Seignette's salt (potassium sodium tartrate), and into Western literature by
Aizu [22].
MAJOR CRITERIA FOR PARAPHASE SEARCH
The paraphase search criteria may conventionally be divided into 'geometric'

and 'physical' ones. The geometric criteria comprise the following.
(1) Determining the symmetry group of the paraphase. As we deal with
subgroup-memory phase transitions, the paraphase symmetry group Go should
be a supergroup of the actual high-temperature phase G. Therefore we should
begin our search for the paraphase by enumerating the supergroups Go 1 , G 02 , ...
of the group G. This can readily be done with the help of tables [11,12].
(2) Determining the paraphase unit cell and its imbedding in the phase
G unit cell. Analyzing the articulation of the lattices of the Go and G phases
gives the wave-vector star describing the hypothetical Go ---+ G transition and
is the first step in the determination of the paraphase structure. To determine
the paraphase unit cell, it is convenient to exploit the concept of the transition
channel (§7). But if tables [11,12] are used in searching for the supergroup Go
of the group G, the transition channel and hence the articulation of the unit
cells are determinable automatically since all the subgroups of the space groups
in these tables are sorted according to the Lifschitz channels.
(3) Determining the paraphase structure. To prescribe the structure of
the paraphase, it is necessary to specify, in addition to the symmetry group of
the latter, also the positions of the multiple points occupied by the atoms of
the crystal. As this is done, the list of possible supergroups Go of the group G
shortens dramatically. In determining the paraphase structure, the following
two important points must be taken into account. First, the hypothetical
Go ---+ G transition is accompanied by displacement of atoms of one species,
whereas atoms of the other species are apt to undergo no displacement from
94 CHAPTER 3
the equilibrium position. Second, at the G -+ G transition some phase Go

multiple-point positions occupied by atoms of one species may split up during
the transition into several positions in the phase G, whereas the other positions
occupied by atoms of the other species undergo no layering - only the symbols
of these positions change.
The simplest way of determining the paraphase structure is by using the
superposition method. The gist of this method is that allowing for the cor-
responding channel of the transitions Go -+ G (that is, the imbedding of the
phase G cells in Go) the images of the positions of the multiple points of all
the supergroups Go of the group G are successively compared with that of the
structure G really observed. In those cases where the paraphase positions un-
dergo splitting at the Go -+ G transition, the following method may be used
[23]. Let the atoms of a given species in the phase Go occupy two positions.
We choose one atom from one position with coordinates (X1Y1Zl) and another
atom from the second position (X2Y2Z2). If there exists a symmetry element g,
not involved in the group G (g ct. G), such that
(10.1)
where u is a small displacement (lui ~ a), then the element g should be part of
the paraphase Go. One should also take account of the fact that the Go -+ G
transition may be accompanied by an atomic ordering. When determining the
paraphase structure one may therefore try to combine, in the sense of equation
(10.1), the positions occupied by atoms of different sorts.
In the general case geometric criteria of the search for the paraphase pro-
vide no unambiguous answer. Further selection from among the remaining
candidates for the role of the paraphase is done on the basis of physical crite-
ria; that is, the domain structure observed in the phase G should correspond to
the symmetry change Go -+ G, Go being the symmetry group of the paraphase.
In the case of an array of transitions Go -+ G 1 -+ G 2 , where G 1 -+ G 2 is the
observed transition and Go the paraphase, the anomalies in the physical prop-
erties at the transition G 1 -+ G 2 should be correctly described by a potential
<1>0 invariant under the paraphase group Go. The phase diagram obtained from
an analysis of the potential <1>0 should coincide with that observed. A detailed
analysis of physical criteria is available in [24] and [25].
AN EXAMPLE OF CHOOSING THE PARAPHASE
We illustrate the procedure of selecting the paraphase by the example of

ammonium sulfate (NH4hS04. At a temperature of about 50°C the structural
transition D~~ ---+ Civ occurs in this compound. One of the features peculiar
to this compound is the occurrence of a complicated domain structure in some
samples at room temperature, that is, in the phase D~~ [26]. It is remarkable
that the angle between the edges of unit cells belonging to different domains
is close to 60 0 • Another feature of the high-symmetry phase in ammonium
sulfate is that by applying small pressures to the sample it is possible to cause
the domain boundaries to move and to bring the entire crystal into a single-
domain state [27].
The above peculiarities of (NH4hS04 have been accounted for on the
assumption that a hypothetical high-symmetry paraphase is present in this
compound [28].
In searching for the paraphase, we base ourselves on the experimentally
determined structure of the phase D~~. According to structure analysis data
[29], the S atoms occupy the position 4(c) of the group D~~ with the parameters
x = 0.250, Y = 0.417, and z = 0.250. The oxygen atoms occupy the positions
4( c) and 8( d). The nitrogen atoms occupy the positions 4( c), the hydrogen
atoms the positions 4(c) and 8(d).
We choose the possible paraphase symmetry groups. These should be
super groups of the group D~~. The presence of sixty-degree domain walls
indicates that we may restrict ourselves to hexagonal supergroups. From space-
group subgroup tables, we find that we may choose as the paraphase symmetry
groups the groups D~~ and D~h which have as their subgroup the group D~~
in channel 2. This channel describes the possible imbedding of the cell fo of
the phase D~~ into the cell fh of the hypothetical paraphase D~h (Fig. 3.11).
Fig. 3.11. Insertion of phase D~~ cell fo into paraphase cell fh

(projection on the basal plane). The symbols af, a!f, and aft stand
for the primitive vectors of the cell fh; the symbols a, b, and c denote
the primitive vectors of the cell fo.
96 CHAPTER 3
In order to choose from the groups D~h the one that is the group of
the paraphase in this compound, we need to determine into which paraphase
multiple-point positions the positions occupied by the atoms in the phase D~~
should pass. Since the sulfur atoms in the phase D~~ occupy one position
4(c), it is with this position that we start our analysis of the transformation
of coordinates at the transition D~~ -> D:;.4. The simplest of the methods is
the geometric one. Using experimental data, we sketch the arrangement of S
atoms in the cell fo as centers of triangles in Fig. 3.12. On comparing the
images of the multiple-point positions of the groups D~h and D~h' we find that
only the position 2( c) of the group D~h' that is, the centers of triangles in Fig.
3.13, coincides with the location of the S atoms. It is the group D~h that was
chosen as the paraphase in [27].
Fig. 3.12. Arrangement of S04 in phase D~~ after [29]. The S atoms
are located within the triangular pyramids. The numerals denote
height . • , oxygen atoms 0(3) 8(d); 0, atoms 0(2) 4(c); the atoms
0(1) 4(c) lie at the vertices of the pyramids. The shaded circlets
represent pyramids with the vertices up.
Analogously it is possible to determine in which positions of the paraphase

the other atoms will be located. In the following we confine ourselves to an
analysis of the oxygen atoms, which allows important conclusions to be drawn
concerning the hypothetical phase transition D~h -> D~~. The location of the
oxygen atoms, constructed according to the data of [29], is depicted in Fig.
3.12. The relative position of the sulfur and oxygen atoms is sketched in Fig.
3.14. It can be readily seen that if the oxygen atoms are displaced by 0.0625A
in the direction shown by arrows in Fig. 3.13, the atoms 0(2) and 0(3) will
occupy in the phase D~h the position 6(h) corresponding to the vertices of the
Fig. 3.13. Pictorial representation of the multiple-point positions

2(c) and 6(h) in the paraphase D~h' *, position 2(c) in group D~h; .,
position 6(h). The numerals indicate height.
triangles portrayed in Fig. 3.13. The dashed line in Fig. 3.12 singles out the
fo cell which coincides with that pictured in Fig. 3.13.
Fig. 3.14. Relative position of Sand 0 atoms in the (NH4hS04

crystal. The arrows show how the 0(2) and 0(3) atoms should be
displaced to form the 6( h) position in the group D~h'
A similar analysis of the transformation of the 4(c) position occupied by

the 0(1) atoms shows that there is no exact analog of this position in the phase
D~h' The closest position of the phase D~h to the 4( c) position occupied by the
0(1) atoms is the position 4(/) of the group D~h' If we rewrite the coordinates
of the 0(1) atoms in the hexagonal system of coordinates, we will readily see that
these atoms occupy only half the 4(/) position. The only way of resolving this
contradiction is by assuming that in the hypothetical phase the orientation of
the tetrahedra formed by the oxygen atoms is random, that is, the probability of
98 CHAPTER 3
the 0(1) atoms being in the 4(f) position is ~. The paraphase thus constructed
enables one to describe the entire set of experimental data on the physical
properties of the phase D~~. Thus the assumption as to the hypothetical phase
transition D~h -> D~~ in (NH 4hS04 accounts for the observed peculiarities
and the occurrence of a domain structure in the phase D~~ that really exists
up to the melting point. Analysis of the paraphase structure has permitted the
important conclusion that the D~h -> D~~ transition should be accompanied by
displacement of the oxygen atoms relative to the sulfur atoms and by ordering
of the orientations of the tetrahedra, as is shown in Fig. 3.12. This means that
the transition D~h -> D~% should be described by at least two interacting order
parameters [28].
The idea of the paraphase has proved constructive in analyzing optical
spectra of complicated compounds. Thus the introduction of a hexagonal para-
phase has made it possible to decode low-frequency combination scattering
spectra of monoclinic sodium trihydroselenite [30].
References
1. S.C. Miller, and W. Love: Tables of Irreducible Representations of Space

Groups and Co-representations of Magnetic Space Groups, Pruett Press
(1967) .
2. C.J. Bradley, and A.D. Cracknell: The Mathematical Theory of Symmetry
in Solids, Clarendon Press (1972).
and Breach (1965).
4. E.M. Lifschitz: Zh. Eksp. Teor. Fiz. 11,255 (1941).
(Neutronography of Magnetics), Atomizdat (1981).
6. V.E. Naish, and V.N. Syromyatnikov: Kristallografiya 21, 1085 (1976).
7. Yu.I. Sirotin, and M.P. Shaskol'skaya: Osnovy Kristallofiziki (Fundamen-
tals of Crystallography), Nauka (1975).
8. Yu.A. Izyumov, V.E. Naish, and V.N. Syromyatnikov: J. Magn. Magnet.
Mat. 12,249 (1979).
9. J .L. Birman: Phys. Rev. Lett. 17, 1216 (1966).
10. Yu.A. Izyumov, V.E. Naish, and V.N. Syromyatnikov: Kristallografiya 21,
256 (1976).
11. V.E. Naish, and V.N. Syromyatnikov: Podgruppy Prostranstvennykh Grupp.
I. Podgruppy s Sokhraneniyem Yacheiki (Subgroups of Space Groups I. Sub-

groups with Preservation of Cells), Dep. VINITI, No. 2371-76 (1976).
12. V.E. Naish, S.B. Petrov, and V.N. Syromyatnikov: Podgruppy Prostranst-
vennykh Grupp. II. Podgruppy s Ismeneniyem Yacheiki (Subgroups of Space
Groups II. Subgroups with Alteration of Cells), Dep. VINITI, No. 486-77
(1977).
13. I.S. Zheludev, and L.A. Shuvalov: Kristallografiya 1, 681 (1956).
14. I.S. Zheludev: Simmetriya i ee Prilozheniya, Atomizdat (1976).
16. K. Aizu: Phys. Rev. 132, 754 (1970).
17. E. Ascher: Helv. Phys. Acta 39, 466 (1966).
18. V. Janovec: Ferroelectrics 12, 43 (1976).
19. Z. Zikmund: Czechoslovak J. Phys. B 34, 932 (1984).
20. V. Janovec: Czechoslovak J. Phys. B 22,974 (1972).
22. K. Aizu: J. Phys. Soc. Japan, 44 683 (1978).
23. S.C. Abrahams, and E.T. Keve: Ferroelectrics 2, 129 (1971).
24. Yu.M. Gufan, V.P. Dmitriyev, and V.I. Torgashev: Kristallografiya 24,597
(1979).
25. P. Toledano, and G. Pascoli: Ferroelectrics 25, 427 (1980).
26. R.M. Cahn: Adv. in Phys. 3, 363 (1954).
27. Y. Makita, A. Sawada, and Y. Takagi: J. Phys. Soc. Japan 41, 167 (1976).
28. A. Sawada, Y. Makita, and Y. Takagi: J. Phys. Soc. Japan 41,174 (1976).
29. E.O. Schlemper, and W.C. Hamilton: J. Chern. Phys. 44, 4498 (1966).
30. V.P. Dmitriyev, L.M. Rabkin, and L.A. Shuvalov: Fiz. Tverd. Tela 22,
1114 (1980).
CHAPTER 4
Analysis of the Thermodynamic Potential
11. Invariant Expressions of the Thermodynamic Potential
A STRAIGHTFORWARD (DIRECT) METHOD OF CONSTRUCTING

POLYNOMIAL INVARIANTS
The phenomenological method of analyzing phase transitions is based on the

construction of a thermodynamic potential <Jl which may be represented as a
polynomial expansion
(11.1)
n
where Pn ( {1],).}) are homogeneous polynomials of degree n invariant under the

initial-phase symmetry group G. The quantities 1]).., which are OP's, transform
according to the group G IR D" responsible for the symmetry change at the
phase transition.
The polynomial Pn = Pn ( .. . 1],). ... ) is invariant under the group G if the
following relation holds for any element g of the group G:
gPn (. . . 1],). ••• ) == Pn(. .. g1],). ... ) = Pn(. . . 1],). ••• ), (11.2)
the action of an element g on the OP components being determined with the

aid of the matrices of the responsible IR:
g1],). = I: DX,).,(g)1],).'·
,).,
(11.3)
In practice, invariant polynomials of degree n may be constructed by writing

the most general expression for a polynomial of a given degree with literal
coefficients and then finding these from equations (11.2). Clearly, not all n(G)
of such equations will be independent, but only those that are obtained when
100
ANALYSIS OF THE THERMODYNAMIC POTENTIAL 101
the generators of the group are used as the elements g. It is only the group
generators that one should take to derive the equations (11.2) which determine
the coefficients of a polynomial. Depending on the ratio between the numbers
n (degree of polynomial), Iv (dimensionality of the IR), and r (number of
generators in the group), part of the initial literal coefficients may turn out
to be indeterminate. The number of these coefficients gives the number of
independent invariant polynomials of given degree Pn.
When desired, this number may be calculated in advance since it coincides
with the multiplicity factor of the group G identity representation involved
in the symmetrized product of the representation [D]n(g) according to which
the product of the quantities constituted by the set {1].>.} should transform.
According to the general formula (2.14),
Pn = n(~) 2)Xt(g). (11.4)

9
Let it be noted that there is only one second-order invariant for the IR DV
and that invariants of degree three exist only for passive representations.
The scheme described above may be illustrated in detail by particular
examples, in which we restrict ourselves to degrees not higher than four.
CONSTRUCTING THE <J> FOR THE STRUCTURAL PHASE TRANSITION IN C-15

COMPOUNDS
We construct polynomial invariants for the group Ok by using the quantities
that transform over the three-dimensional IR 77 with", = 0 (this representation
describes the structural transition in the superconducting compounds HfV 2 and
ZrV 2 , which belong to the class of C-15 compounds).
From the Kovalev tables, we write out the matrices of the group oI gen-
erators, choosing as the latter the group Ok zero-block elements h5, h14' and
h 25 :
V(h,) = G 1
o D(h14) = (0I 1 0)
0 ~ , V(h,,) = G
o
1 0
0) .
o 001 o 1
According to equation (11.3), we may write the operation of these elements on
the OP components:
h 5 1]1 = 1]2, h 14 1]1 = 1]2, h 25 1]1 = 1]1,
h 5 1]2 = 1]3, h 14 1]2 = -1]1, h 25 1]2 = 1]2, ( 11.5)
h 5 1]3 = 1]1, h 141]3 = -1]3, h 25 1]3 = 1]3·
102 CHAPTER 4
With the help of these equations, we check that the expression
P2 = 1Ji + 1J~ + 1J~ (11.6)
is invariant.
Now we construct third-degree polynomials of the most general form
P3 = vI1Jf + V21J~ + V31J~ + V41Jr1J2 + VS1Ji1J3 + V61J~1Jl +

+V71J~1J3 + Vs1J~1Jl + V91J~1J2 + Vl01J11J21J3' (11.7)
On acting with the element hs on P3 and equating the result to P3 , we

obtain the following relations between the coefficients:
On acting additionally with the element h14' we obtain the new equations:
VI = V4 = V5 = O. Thus only one term remains invariant with respect to the
elements h5 and h 14 :
P3 = 1JI1J21J3· (11.8)
Consider the fourth-degree polynomial
P4 = UI1J{ + u21Ji + U31Jj + u41Ji1J~ + U51Jr1J5 + U617~175+

+u717f172 + uS17f173 + U917~1Jl + Ul01J~1J3 + Ull1J~171 + UI217~1J2' (11.9)
The equation h 5 P4 = P4 yields the following relations among the coefficients:

Ul = U2 = U3, U4 = U5 = U6, Us = U9 = U12, U7 = UI0 = Ull. The
equation h 14 P4 = P4 gives, in addition to them, one more relation: h7 = Us = 0,
so that the invariant expression for P4 has the final form
(11.10)
Summing the results (11.6), (11.8) and (11.10), we represent the invariant
expansion of the thermodynamic potential as
<P = r( 1Ji + 17~ + 1J~) + V171 172173+

+Ul(1J{ + 17i + 1Jj) + U2(17i17~ + 1Jr1J5 + 17~175)· (11.11)
CONSTRUCTING THE <P FOR THE STRUCTURAL PHASE TRANSITION IN A-15

COMPOUNDS
We consider the group O~, the two-dimensional representation 7"5 for K, = 0 (this
representation describes the structural phase transition in the superconducting
compounds Nb 3 Sn and V3 Si from the class A-15).
The matrices of this IR are given in Table 2.5. Choosing the elements
and h25 as the generators of the group, we write, by means of the
h 5 , h14
corresponding matrices of the representation, the result of their action on the
two OP components, 111 and 112:
(11.12)
(the element h25 does not alter the OP).

Consider a second-degree polynomial of the most general form:
The equation h 5 P2 = P2 leads to the relation r1 = r2, and the equation h 14 P2 =

= =
P2 results in the relations ri (2 ri and ri ( ri, which are satisfied only when
ri = O. Thus an invariant second-degree polynomial is
(11.13)
For the general third-degree polynomial
we have the relations Vi = V2 and V3 = V4 resulting from the equation h 14 P3 =

P3 . We now operate on P3 with the element h5:
Equating this result to P3 yields two equations, (V3 = V3 and (2V3 = V3, which
are simultaneous if V3 = O. Thus the invariant third-degree polynomial has the
form
P3 = 11~ + 11~. (11.14)
For the fourth-degree polynomial
the action of the element h14 gives Ui = U2 and U4 = U5. Acting with the
element h5 on the polynomial obtained, we find additionally Ui = 0 and U4 = o.
We obtain the only invariant fourth-degree polynomial
(11.15)
104 CHAPTER 4
Thus up to fourth degree the invariant expansion of the thermodynamic po-

tential is
;r,. _
'l' - r'fJ1 'fJ2 + V (3 3) 2 2
'fJ1 + 'fJ2 + U'fJ1 'fJ2 • (11.16)
It is evident that by linear transformation, the quadratic term may be brought

into diagonal form, so that in the new variables all the invariants alter in form.
Thus we go from the set of variables 'fJ).. on to another set 6 ('fJ = Ue) by means
of the unitary matrix U:
U= V2
1 (1 1 (11.17)
The explicit form of this linear transformation
'fJ1 = ~(6 - i6), 'fJ2 = ~(6 + i6) (11.18)
shows that the expression for cI> remains real if e1

and 6 are real quantities. It
is these quantities that may serve as the OP's for the corresponding physical
system. In these variables the expression (11.14) becomes
(11.19)
with r, v, and u being some real-valued coefficients.
12. Integral Rational Basis of Invariants
GENERAL REMARKS
Landau's phenomenological theory presupposed an exploration of a shortened

series for the expansion of the thermodynamic potential in a power series of
the OP, and for most of the problems solved it sufficed to allow for degrees not
higher than four. Later in the text, however, we shall encounter examples where
a complete thermodynamic analysis of a phase transition necessitates allowance
for higher-order expansion terms. A typical drawback of the 'fJ4 model, as will
be seen in the section that follows, is that some low-symmetry solutions of
energy-minimizing equations are lost. Such solutions are often of not only
theoretical but also practical interest, for example in instrument making, since
low-symmetry states are, as a rule, very sensitive to external effects. On the
other hand, as we shall see, in order to construct a complete phase diagram of
a system and to analyze the stability of all its phases, it is necessary to allow
for higher-order expansion terms.
Thus the problem arises of constructing quintic, sextic, and higher-order

polynomial invariants. As is seen from the standard method outlined in §11,
the scope of calculations needed to construct polynomial invariants grows dra-
matically with increasing degree of polynomial. Therefore it is necessary to
have a more efficient method that permits ascertaining simultaneously also the
structure of the whole series, particularly specifying the number of independent
invariants of a given degree.
At the end of the last century and at the beginning of this century the
mathematicians Gordon, Hilbert, Weyl, Noether and others proved that for
certain abstract groups (which turn out to include also crystal space groups)
there exists a finite set of independent polynomial invariants in terms of which
any invariant may be expressed as a rational function of invariants from that set.
Such a finite set of independent invariants has come to be called an integral
rational basis of invariants (IRBI). The problem of constructing a complete
series for the thermodynamic potential thus reduces to one of building an IRBI
for the symmetric group of the initial phase.
A more comprehensible exposition of the abstract IRBI theory for physi-
cists is given in Spencer's book [1]. A large contribution to the development
and application of IRBI methods has been made by the numerous papers of
Smith and Rivlin [2], Green and Adkins [3]. Using polar-vector components
and a tensor of rank two, the authors of [3] have constructed an IRBI for the
crystal point groups. During [4] has done the same for the axial vector. In
[1] a large variety of examples are provided. The construction of IRBI's for
the crystal space groups was first carried out by Gufan and Sakhnenko [5,12]'
Michel, Morzymas, and others [6,12,13,19]. In what follows we outline a work-
ing scheme of constructing IRBI's that is convenient for work with the space
groups [7].
THE IRBI CONSTRUCTION ALGORITHM
A central concept of the theory is the notion of the kernel of a homomorphism.

Suppose that we are given one of the representations DII of the group G. This
means that some matrix DII (g) is associated with each element belonging to
the group G. The identity element is put in correspondence with the identity
matrix of dimension Ill' We now choose from all the elements g of the group
G those whose representation DII matrices coincide with the identity matrix.
We denote the given set of group G elements by H. The set H is a normal
subgroup of the group G (that is, H <J G), and this subgroup is called the kernel
106 CHAPTER 4
of the homomorphism of the representation DV. We now decompose the group

G into cosets relative to the subgroup H:
(12.1)
gi being the representatives of the decomposition. The cosets = giH of the

ai
group G form a factor group G H = G / H, constructed from the homomorphic

kernel H of the representation DV. We place each element ai in correspondence
with the matrix d V (gi) and thus obtain the irreducible representation D V ofthe
group GH. Obviously, if invariant under the group GH:
aP( ... Cr···) = P( ... cr·· .),

the polynomial P( . .. cr ... ) will be invariant under the group G too.
Thus the problem of constructing polynomial invariants for the represen-
tation D V of the space group G, whose order is equal to N (G), reduces to one
of constructing polynomial invariants for the abstract group 1 that is isomor-
phic to the factor group G H and is constructed from the homomorphic kernel
H of the group G representation DV. The group 1 is prescribed by different
matrices DV(gi) of the group G representation DV. In the literature the group
1 is normally referred to as the image of the IR (the term was introduced by
the authors of [6]).
The number of elements in the group 1 may be still larger and it is a
challenge to construct an IRBI for this group. However, this problem can
be broken up into several finite steps, reducing the whole problem to one of
constructing an IRBI for a very simple group. We introduce the concept of a
normal series of the group 1, that is, a subgroup array [8]:
(12.2)
where G n is a normal subgroup of G n +1 . The factor groups GdG 2 , G 2 /G 3 ,
G 3 /G 4 , ... are called the factors of a normal series.
Now we wish to see how the IRBI for the group 1 itself can be constructed
if one knows the IRBI relative to a normal subgroup H' of the group 1 (H' ~I).
Assume that we are given some representation D = { ... D( a) ... } of the group
1 of finite order N(I). The normal divisor of the group 1 is the subgroup
H' ~ 1 of order N(H'). In terms of h, 12 , 13 , ••• we denote the IRBI relative to
the group 1 for the given set of quantities C 1 , C 2 , C3 , ... Cc, which transform
according to the representation D = { ... D(a) .. .}, where a E 1, as follows:
aC>. = E D>'I-'(a)C,... (12.3)

I-'
The restriction of the representation D of the group I to the subgroup H' is

denoted by
D(S) = { ... D(b) .. .}, bE H.
Let :11, :12, :13, ... be an IRBI with respect to the variables 0 1, O2,03, .. . Oz
transforming according to the representation D(S) of the group H'.
Let us see how the quantities :11, :12, ... transform under the action of the
elements a E I. We partition the group I into cosets relative to the subgroup
H':
(12.4)
L L
where OL are the representatives of the decomposition. For any element a

belonging to the coset OLH we have
(12.5)
If :lp is an invariant under the group H', the quantity 0 L:lp = :1//) will also
be invariant under H' and obey equation (12.5).
We take now any invariant Iq from the IRBI of the group I. The quantity
Iq is invariant under the action of any element of the group I, specifically under
the subgroup H'. Therefore Iq may be represented as a polynomial in the group
invariants:
(12.6)
Consequently, the polynomial P(lt ,12, ... ,IG) == P( {Iq}) may be represented
in the form
(12.7)
Consider the case when the order of the factor group 1/ H' is equal to two:
I = H' + 0 H' = H' + H' O. (12.8)
Denote O:lp = :I;. Using equations (12.5), we see that
(12.9)
The expression (12.7) then assumes the form
(12.10)
108 CHAPTER 4
The requirement that the polynomial P'( {..1p }, {..1;}) be invariant under the
group I, as follows from equation (12.9), resides in the equation
(12.11)
On denoting
..11 = U1, ..12 = V1,···, ..1H = Zl; (12.12)
..1{ = U2, ..1~ = V2,· .. , ..1iI = Z2,
the expression (12.11) may be rearranged to read
(12.13)
N ow we can use Theorem 1.
Theorem 1 [1,3]. The IRBI for polynomials in variables (U1,V1,W1",.,Zl,

U2, V2, W2, ... , Z2) invariant under the permutation of the indices 1 and 2 con-
sists of the elements
On the basis of this theorem as well as equations (12.12), we may write

the IRBI for the group I in terms of the invariants of its normal subgroup H':
II = Ul + U2 = ..11 + ..1{; 12 = VI ~ V2 = ..12 + ..1~; ... }

(12.14)
IG = ZlZ2 = ..1H..1H
Consider now the case where the factor group I JH' is of order 3, that is,
N(I)JN(H') = 3. Decompose the group I into cosets relative to the subgroup
(12.15)
The multiplication table for the factor-group elements has the form
H' G1H' G2 H '

H' H'
GIH' G2H'
(12.16)
G1H' GIH' G2H' H'
G2H' G2H' H' GIH'
Using the expressions (12.15) and (12.16), we can write the operation of the
group I elements on the quantities {.1l, .12, ... ,.1H}:
H'{.1p } = {.1p }, Cl H'{.1p } == {.1P)}, C2H'{.1p } == {.1P)}; (12.17)
C l H'{.1P)} = {.1P)}, C2H'{.1P)} = {.1p },

(12.18)
C l H'{.1P)} = {.1p }, C2H'{.1P)} = {.1P)}·
Just as in the previous examples, the polynomial P(h, 12 , .•• , 1G) may be rep-
resented as
P(Il,h, ... ,IG) = p'({.1p }, {.1P)}, {.1P)})· (12.19)
The invariance of the polynomial (12.19) under I implies that
pi ({.1p }, {.1P)}, {.1P)}) = pi ({.1P)}, {.1P)}, {.1p }) =
= pi ({.1P)}, {.1p }, {.1P)}). (12.20)
In equation (12.20) we set
(12.21)
Equations (12.20) imply that the polynomials are symmetric with respect to a
cyclic permutation of the arguments {Ul, Vl, ... }, {U2, V2, ... } and {U3, V3, ... },
so that Theorem 2 may be applied.
Theorem 2. The IRBI for polynomials in ths system of variables (Ul, Vl, Wl, ... ,
Zl, U2,V2,W2, ... ,Z2, U3,V3,W3, ... ,Z3) invariant under a cyclic permutation
of the indices 1,2,3 consists of the elements
Ul + U2 + U3, Ul U2 U3, Ul U2 + Ul U3 + U2 U3,

UlU2(Ul - U2) + U2U3(U2 - U3) + U3Ul(U3 - Ul)
and the expressions resulting from them by substituting Vi, Wi,"" zi for Ui:
Ul Vl + U2V2 + U3V3, Ul U2V3 + U2U3Vl + U3Ul V2,

UlV2 V3 + U2V3Vl + U3VlV2, Ul(V2 - V3) + U2(V3 - Vl) + U3(Vl - V2),
UlU2(Vl - V2) + U2U3(V2 - V3) + U3Ul(V3 - vd,
VlV2(Ul - U2) + V2V3(U2 - U3) + V3Vl(U3 - ud,
110 CHAPTER 4
the expressions resulting from them by substituting for Ui, Vi the various com-
binations of two different symbols chosen from (Uj, Vi, Wi, ... , Zi):
and the expressions resulting from them by substituting for Ui, Vi, Wi the various
combinations of three different symbols chosen from (Ui' Vi, Wi, ... , Zj).
Returning to the notation (12.21), we may write the IRBI for the group I
(12.15).
From the above examples, it becomes clear how the IRBI is constructed
from the quantities C).. transforming according to the initial-phase symmetry
group IR DV. The IRBI construction procedure boils down to the following
stages.
1. From the table of space group representations, we write out the matrices
of the representation DV.
2. From among the group G elements, we choose those whose matrices in
the representation D V coincide with the identity matrix. We thus obtain the
kernel of homomorphism H.
3. We construct the factor group PH = G / H. In practice, we should
simply choose from all the representation F V matrices all the distinct matrices
and label the latter by DV(a). Multiplying the matrices DV together, we then
make up a Cayley square (compile a multiplication table) which enables us to
determine the abstract group I isomorphic to the factor group GH.
4. The resulting group I is expanded in a normal series (12.2).
5. Starting from the last term of the series, we express the invariants
for the higher-order term through the lower-order terms until we arrive at the
group I of interest.
SOLVABILITY OF THE GROUP AND THE MINIMAL IRBI
The method described above is applicable to what is called solvable groups. A

group G is said to be solvable if it is representable as a normal series and if the
latter may be so chosen that all the factor groups in this series are isomorphic
to abelian groups. The latter circumstance, however, is not used in explicit
form in the construction of the IRBI.
We wish to show that all the I groups corresponding to the Brillouin
zone symmetric-point IR's of all the space groups are solvable. Any group I
is specified by a set of different zero-block element matrices and initial-space-

group translation matrices. The maximum number of elements in a group
I is equal to 48 x 32 = 1536 where 32 is the maximum number of different
translations, which corresponds to a maximum possible increase in primitive
cell volume at the phase transition. This origin of the I groups results in the
fact that the order of these groups may always be represented as 2"3 13 , where
00 and f3 are integers.
The following theorem has been proved in group theory.
Theorem 3 (Burnside's theorem [8]). The group G of order N( G) is solvable

if N(G) = p"q13, where p, q are prime integers and 00, f3 non-negative integers.
From Burnside's theorem and from what has been said above, it follows
immediately that the I groups are solvable.
Now we discuss the problem concerning the minimality of the IRBI. By
a minimal IRBI (MIRBI) one means a set of polynomial invariants in which
none of its terms may be expressed as a polynomial in the other terms of the
given set. At each IRBI construction stage one obtains several invariants of a
given degree, some of which may be represented as polynomials in lower-degree
invariants. These invariants should be cancelled out as not being involved in
the MIRBI. Such choice should be made at each stage of the construction of
an IRBI for a given I group.
In determining independent invariants of a given degree, it is useful for ver-
ification to calculate the number of independent invariants. The total number
of invariants Np of degree p is equal to the multiplicity factor of the identity
representation involved in the pth degree of the IR considered. The Np can
evidently be found using the formula
(12.22)
where G is the symmetry group of the initial phase and X(g) the character of
the IR explored.
From the total number of invariants of a given degree N p , we need to sub-
tract those that may be represented as polynomials in lower-degree invariants.
The number of these invariants is determined by simply making an exhaustive
search. Finally, it is necessary to exclude from the remaining invariants those
that are related to lower-degree invariants in a non-polynomial fashion, that
is, those due to a so-called syzygy [1). For example, if an invariant I of degree
112 CHAPTER 4
p cannot be expressed as a polynomial in lower-degree invariants, while the

square of that invariant ]2 is representable, then the given invariant is not
an independent one, and its relation to other invariants is called the syzygy.
The number of syzygies will be labeled by N;'. As a result, the number of
independent invariants generating the MIRBI for a given group is
N Pmin -- N P - N'P - Nil

p. (12.23)
Finally, when searching for the MIRBI, we may immediately discard in-
variants whose degree is higher than the order of the given] group. We may
do so by virtue of Theorem 4.
Theorem 4 (E. Noether). The degree of IRBI elements for polynomials in-
variant under a finite transformation group does not exceed the order of that
group.
13. Examples of the Construction of an IRBI
CONSTRUCTING THE IRBI FOR THE STRUCTURAL TRANSITION

IN C-15 COMPOUNDS
We wish to construct the IRBI for the group oXfrom which the phase transition
takes place according to the representation with K, = 0. We start by finding the
kernel of the homomorphism of the representation T7. The zero-block matrices
of the representation T7 are given in §11, where it is shown that the kernel of
the homomorphism H in our case coincides with the space group Gl. Indeed,
the matrices of the representation T7 for the elements {h110}, {h 25 Ir}, {h1It n },
where tn is any translation and T a fractional translation, coincide with the
identity matrix. The point group ], isomorphic to the factor group G H, is
specified by a set of twenty-four different representation T7 matrices and, as
can be readily seen, coincides with the point group T d • Let a; label a group
] = Td element assigned by the matrix D(g;) of the representation T7. For
example, the element corresponds to the matrix
D(g5) = D({h 5 10 00}) = ( 0

~ ~1 001)
of the representation T7.

The next step, according to the IREI construction procedure oulined, is

to expand the group Td in a normal series:
The normal series terms may be chosen in the form
= C2 = {a1, a2}, G2 = D2 = C2 + a3C2,

G3
G1 = T = D2 + a5D2 + a9D2, 1 = Td = T + a13T. (13.2)
At the outset we find the IRBI for the group G 3 = C2 • In doing so, we
shall take account of the fact that according to Noether's theorem the maximal
degree of the polynomial invariants involved in the IREI does not exceed the
order of the group N(G3 = C2 ) = 2.
We denote the variables transforming according to the representation 77
by "11, "12, "13· We let the operator a2 act on these variables: a2("I1,"I2,"I3) =
("11,-"12,-"13). We introduce the variables U1 = "12, U2 = -"11, V1 = "13, V2 =
-"13 and set "11 = h,3' According to Theorem 1, the IREI for the group G 3
may be written in the form
(13.3)
We now construct the IREI for the group G 2 = D2 = C2 + a3C 2. Note

that a3("I1,"I2,"I3) = (-"11,"12,-"13). Then we have from equation (13.3)
We introduce the variables U1 =

h.3, U2 = -h.3, V1 = 14 .3 , V2 = -14 .3 . From
Theorem 2 we obtain the IRBI for the group G2 :
(13.4)
A further step is to construct the IREI for the group G 2 = D2 + a5D2 +

a9 D 2. As a5("11"12"13) = ("12,"13,"11) and a9("I1, "12, "13) = ("13,"11,"12), it follows
from equation (13.4) that
a5h.2 = h.2, a5 12.2 = 13.2, a5 13.2 = h.2, a5 14.2 = 14.2

a9h.2 = 13.2, a9 12.2 = 11.2, a9 13.2 = h.2, a9 14.2 = 14.2.
114 CHAPTER 4
We denote U1 = 11.2, u2 = a5I1.2 = 12.2 , u3 = a9I1.2 = 13.2 and obtain, accord-

ing to Theorem 2, the IRBI for the group G 1 :
I _ 1-22
I Ll = 1112 + r122 + TJ3'2 2.1 - TJ1TJ2TJ3, 3.1 - TJ1TJ2 + TJ1TJ3
22
+ TJ2TJ3'
22
I 4.1 = TJ12 TJ22 (2

TJ1 - TJ22) + TJ22 TJ32 (2
TJ2 - TJ32) + TJ32 TJ12 (2
TJ3 - TJ12) . (13.5)
Finally, we construct the required IRBI for the group Td = T+a 13 T. Since
a13(TJ1,TJ2,TJ3) = (TJ2,TJ1,TJ3), we have, according to equation (13.5), a13h1 =
ILl, a13 I2.1 = 12.1> a13 I3.1 = 13.1, a13 I4.1 = -14.1, Denoting U1 = 14.1 and
U2 = a13I4.1 = -14.1, we obtain one more invariant of the group Td : 14 = IL
(along with the three invariants present: h = ILl, h = h1' and 13 = hI).
Being reducible, this invariant is not part of the IRBI. Indeed, assume that
the invariant 14 = IJ.1 is not independent, that is, is polynomially expressed in
terms of the invariants II, 12 and 13 , Allowing for the degree of all the four
invariants, we write this relation in general form with some coefficients to be
defined:
Using the explicit form of the invariants and equating the coefficients of like
degrees of the basis functions, we obtain A = 0, B = 0, C = -4, D = I, E =
-15,F = 2, G = 2, so that
Thus the IRBI of the problem consists of three invariants:
(13.6)
Let us compare this conclusion with the results of the straightforward

polynomial invariant calculation performed in §11 for the same problem. As
is seen from the formula (11.11), the straightforward method yields as many
as four invariants in the terms of the invariant expansion of the potential .
Three of them coincide with the IRBI, while the fourth originates from the
square of the lowest invariant h.
CONSTRUCTION OF THE IRBI FOR THE STRUCTURAL TRANSITION IN A-15

C01VIPOUNDS
Our goal is to construct the IRBI for the group O~ using the OP components
that transform according to the IR T5 with", = O.
For this case an invariant expansion of the thermodynamic potential up

to the fourth degree in 1] was constructed with the help of the straightforward
method in §11. Now we will show that of the three invariants found there, the
two first invariants, determined by equations (11.13) and (11.14), constitute
the IRBI of the problem under consideration.
We write out six different matrices of group O~ representation 1"5, which
generate an I group (Table 2.5):
a1 (~ ~) , a2 (~ €20) ' a3 0 C
2 €~) ,
a4 C~ ~) , a5 (~ €2) (0
o ' a6 1 o1) .
(13.7)
By simply multiplying the matrices together, we can readily compile a

Cayley square for this group:
a1 a2 a3 a4 a5 a6
a1 a1 a2 a3 a4 a5 a6
a2 a2 a3 a1 a5 a6 a4
as as a1 a2 a6 a4 as (13.8)
a4 a4 a6 a5 a1 a3 a2
as a5 a4 a6 a2 a1 as
a6 a6 a5 a4 as a2 al
Here at the intersection of a row and a column an element is written that is

the product of the elements corresponding to the given row and column. From
the Cayley square we see that the elements al and a3 are of third order, and
the elements a4, a5 and a6 are of second order since
(13.9)
The I group (13.7) is isomorphic to the point group Csv . Indeed, the group Csv
contains two third-order elements, H3 and Hs (rotations about the 3 axis), and
three second-order elements, H 19, H 21, H 23 (reflection planes passing through
the 3 axis). If we denote the elements of the group C3v by the symbols
we can readily see that the Cayley square for the group C3v coincides with that
for the group (13.8), which proves the isomorphism of both groups.
116 CHAPTER 4
Consider the cyclic subgroup
(13.10)
and split the group I into cosets:
(13.11)
Thus the group G 1 is a normal subgroup of the group I. We start by con-

structing invariants for the group G 1 . Since the order of the group G 1 is equal
to three, the degree of the polynomial invariants for it does not exceed three
by virtue of Noether's theorem. In this situation it is most reasonable to find
these by the straightforward method, as was done in §11. The three lowest
invariants of the group G 1 are
(13.12)
We now act on these invariants with the representative element g6, allowing
for the fact that g6"11 = "12, g6"12 = "11:
The first equation indicates that the quantity h = :h is an invariant of the

group I. We set
In keeping with the Theorem 1 outlined in §12, it is the quantities
that should be invariants of the group I. (The other possibilities enumerated

in this theorem lead to the same invariants.) Denote one of the invariants
obtained: h = .:12 + .:l3. It is easy to see that the other two are expressed in
terms of hand I2:
Thus there are two independent invariants:
(13.13)
and it is these invariants that form the IRBI. On comparing this conclusion
with the results of §11 (11.14), we see that the fourth-degree invariant reduces
to If, that is, it is not involved in the MIRBI.
CONSTRUCTING THE IRBI FOR THE STRUCTURAL TRANSITION IN MnAs

The two preceding examples illustrate the construction of the IRBI from the
OP components that transform according to an IR with K. = O. As an ex-
ample of finding the IRBI that describes the transition with K. -:j:. 0, from the
OP components, we construct the IRBI for the structural transition in MnAs.
This transition is described by the one-dimensional IR 7"4 belonging to the star
{K.12} wave-vector group of the hexagonal lattice of the initial phase D~h [9].
The {K.12} is a three-arm star; to find the I group, it is therefore necessary first
to induce from the small representation 7"4 3 x 3 matrices of the large represen-
tation 7"4{K.12} using the formula (2.7). Simple calculations show that the large
representation 7"4 {K.12} is composed of forty-eight different three-dimensional
matrices; consequently, the I group, isomorphic to the factor group GH con-
structed from the kernel of homomorphism H, coincides with the point group
Oh·
The normal series for the group I = Oh has the form
I :J G 1 :J G 2 :J G 3 :J G 4 :J G 5 = E,
(13.14)
I = Oh, G1 = 0, G2 = T, G3 = D2, G4 = C2 •
The terms of the normal series (13.14) are chosen as
I = G 1 + a25G1, G 1 = G 2 + a13G2,
(13.15)
G2 = G3 + a5G3 + a9G3, G 3 = G4 + a3G4, G4 = {a1,a2}.
The matrices corresponding to the elements a1, a2, a3, a5, a9, a13, a25 have
C00) C 0 0) C' ~ ) , a, (~
the form
a1 o 1 0 ,a2 0 -1 o , a3 0 1
0
01,
1 0)
C 0) C ~J
o 0 1 0 0 -1 0 0 -1 1 o 0
a, G 1)
-1 0
(13.16)
o 0 ,a13 -1 0 o ,a25 0 -1
1 0 0 0 -1 0 0
Exploiting the theorems of §12, we find the form of the invariants that
generate the required IRBI:
I1 = Til2+ 2
'f/2 + 'f/3' 2 = 'f/1 'f/2 + 'f/1 'f/3 + 'f/2 'f/3' 3 - 'f/1 'f/2 'f/3·
212222221_222 (13.17)
118 CHAPTER 4
From the example considered above, we see that the procedure of con-
structing the IRBI in the case of n, # 0 (for the Brillouin-zone points) is virtu-
ally no different from the case n, = O.
14. Irreducible Representation Images and

Thermodynamic Potential Types
GENERAL INFORMATION ON THE I GROUPS
As we saw, a group-theoretic analysis of phase transitions reduces, for the most

part, to the problem of exploring the corresponding IR of the parent symmetry
group. As was shown in §12, a set of distinct IR matrices constitutes some
abstract I group. The important role of these groups in phase transition theory
was first noted in [5], where they were called L groups.
We saw that the I group of a given IR may be used to construct polynomial
invariants made up of OP components, that is, to find the form of the thermo-
dynamic potential. Another important feature of the I groups, also noted for
the first time in [5,10]' is that using these groups permits the problem oflisting
all the dissymmetric phases liable to occur as a result of a phase transition
according to a given IR to be solved in a different way.
This problem was encountered earlier in Chap. 3. In solving it, we pro-
ceeded from the real symmetry of the crystal, considering all the subgroups
of the initial-phase space group. From the condition that the dissymmetric-
phase density function 6p be invariant under one of the subgroups, we found
ratios for mixing coefficients TJ>. of responsible-IR basis functions, ratios deter-
mining a specialized set of quantities TJl, TJ2, •.. ,TJI", namely, OP components.
For all the dissymmetric phases to be enumerated, it suffices to enumerate
all such different sets (different mixing coefficient types). For example, in the
case of a three-component {TJITJ2TJ3} OP the following mixing types are possi-
ble: (TJ 0 0), (TJ TJ 0), (TJ TJ TJ), (TJl TJ TJ}, etc. Evidently, each specialized set
may in the general case be treated as the symmetry-isolated direction of an [,,-
component vector 'l1 = {TJ1, TJ2, ... , TJI,,} in an l,,-dimensional OP space. These
vectors transform into each other under the action of distinct vth-IR matrices,
that is, under the operation of I group elements. Each special (symmetric) dir-
ection of the vector 'l1 remains invariant under the operation of some subgroup
of the I group. Thus it becomes clear that the problem of listing the phases of
different symmetry, which arise in a phase transition over a given IR, reduces
to one of enumerating all the subgroups of the I group.
Thus, on determining the corresponding I group, we can reduce the entire

ensuing problem of exploring the phase transition (construction of thermody-
namic potential and determination of possible phases) to working with this
abstract group. As will be seen below, an advantage of this approach mani-
fests itself in a general analysis of possible thermodynamic potential types. In
the present section, as before, we discuss only those IR's that are numbered
by Lifschitz stars. As a result of this restriction, the representations involved
contain a finite number of distinct matrices. The maximal number of distinct
matrices in an IR may be equal to 48 x 32 = 1536, where 48 is the maximal
number of space-group zero-block elements and 32 is the ma.x.imal increase in
primitive cells at phase transitions over Lifschitz stars. In principle, having IR
tables for all space groups, it would be possible to indicate the appropriate I
group for each representation with a Lifschitz star. However, such work has
not yet been carried out, so we wish to adduce a number of considerations that
show which of the I groups are likely to arise in the theory of phase transitions
in crystals.
First, the I groups are isomorphic to the symmetry point groups in lv-
dimensional space [11]. However, of the many abstract groups of this type,
we encounter in space group representation theory only those that contain
rotations by angles equal to 2;,where n = 2,3,4,6,8,12. Rotations with
n = 8,12 arise from space group IR matrices for Lifschitz stars at the expense
of 'lost' translations.
Another important feature of the I groups is that they should have, among
the IR's of specified dimensionality, a vector representation. Obviously, this
follows from the definition of the I groups as the image of an IR.
In the following we provide more detailed information about the I groups
of two-dimensional, three-dimensional and higher-dimension IR's.
Two- AND THREE-COMPONENT ORDER PARAMETERS
Consider the two-dimensional space of the order parameter. Of the various

two-dimensional point groups, we should choose, as the I groups, those whose
two-dimensional vector representation is reducible. This condition is satisfied
by the groups Gn and Gnv with n = 3,4,6,8, 12. From this, it may be de-
duced immediately that anyone of the possible phase transitions with a two-
component OP is described by one of the ten thermodynamic potentials. To
find the explicit form of these potentials, it is necessary to construct the IRBI
for the ten groups Gn and Gnv .
120 CHAPTER 4
The IRBI for the groups C3 and C3t1 were obtained in §13. For the group
C 3 the IRBI consists of three invariants:
2 -- 1/13 - 31/17'122, I 3
11 -- 1/12+ 1/22 , 1 = 1/23 - 2 .
31/11/2 (14.1)
The IRBI for the group C3t1 is composed of two invariants:
(14.2)
It is not difficult to construct the IRBI for the groups C4 and C4t1 . The
subgroup C4t1 may be decomposed into cosets relative to the subgroup C4 :
C 4t1 = C4 + 91C4, where 91 is the reflection in the plane parallel to the tetrad
axis. The group C4 may be represented also as C4 = C2 + 92C2, where 92 is a
rotation by 90° about the tetrad axis. The group C2 consists of two elements
C 2 = {g3, 94}, where 93 is an identity element and 94 = 9~.
Straightforward verification readily shows this decomposition of the group
C4t1 to be an expansion in a normal series. Therefore, in keeping with the
recommendations of §12, we begin the construction of the IRBI with the group
C 2 • Regarding 1/1 and 1/2 as the components of a two-dimensional vector, we
find according to Theorem 1 of §12: :11 =
1/~, ':12 =
1/~, .:13 =
1/11/2. Allowing
for the action of the element 92 on the resulting invariants .:11,2,3, we find the
IRBI for the group C 4 : -
(14.3)
Finally, the IRBI for the group C4t1 is
(14.4)
The IRBI for the other groups Cn and Cntl are found in a similar way.
= =
Passing over to trigonometric notation, 1/1 1/ cos <p and 1/2 1/ sin t/J, the IRBI
for the groups Cn and Cntl may respectively be written as [12]
(14.5)
(14.6)
We now proceed to discuss the three-component OP. Of the various point

groups realized in three-dimensional space, only five groups, T, Td, Th, 0 and
Oh, have three-dimensional irreducible vector repesentations. The IRBI of

these groups are formed from the blocks
11 -_ 1Jl2 +2 2 [_ 1_444
1J2 + 1J3, 2 - 1J11J21J3, 3 - 1Jl + 1J2 + 1J3,
(14.7)
I 4 = 1Jl4( 1J22 - 1J32) + 1J24( 1J32 - 1Jl2) + 1J34( 1Jl2 - 1J22)
and have the form
T(h,hfa,I4), Td(Il,I 2,I3),

Th(h,I3,I4,Ii),O(h,I3,Ii,I2I4), (14.8)
Oh(h, fa, Ii)·
A MULTICOMPONENT ORDER PARAMETER
Further analysis of the I groups reduces to working with multidimensional

point groups, the mathematical machinery of which has been developed to a
considerably lesser extent than that for two-dimensional and three-dimensional
groups. Therefore this method of deriving I groups, employed earlier in an OP
space with 1/1 = 4, proves to be practically inapplicable without prior tabulation
of multidimensional point groups.
Currently, no exhaustive tables of four-, six-, and eight-dimensional I
groups are available in the literature. Existing tables of multidimensional I
groups have been created either for some classes [14] or for describing phase
transitions of a particular type [16,17]. As stated in [11], there exist as many
as thirty-six four-dimensional I groups (a total of thirty-four groups according
to [15]). The lowest order of these groups is equal to 8, and the highest is 384.
I groups whose order exceeds 48 arise in the case of transitions with K, f. 0
owing to space group IR matrices corresponding to translations that are not
preserved in the new phase.
From an analysis of the IR's of all of the 230 space groups numbered by
Lifschitz stars, the authors of [17] revealed thirty-two six-dimensional I groups,
of which the order varies from 48 to 1536.
I GROUPS AND ROTATION GROUPS IN MULTIDIMENSIONAL SPACE
In analysing phase transitions, it very often suffices to deal with the poten-
tial's broken polynomial series that allows for terms of degrees not higher
than four in the OP. Introducing the concepts of the OP space, of the vector
11 = (1Jl, 1J2, .. . 1JI.,) in this space, and of the I groups permits enumeration of all
122 CHAPTER 4
possible model potential types without making an exhaustive search for all the
space group IR's but proceeding from the symmetry of the OP space. Thus,
for example, all the types of potential in the 'fJ4 model for a four-component
OP were derived in [15].
As already stated in the beginning of this section, all the I groups that arise
in the analysis of phase transitions should be subgroups of the rotation group
O(lv) in lv-dimensional space and these subgroups should have irreducible vec-
tor representations. In keeping with [15], we call these subgroups irreducible
subgroups. For example, irreducible subgroups of the three-dimensional ro-
tation group are the groups of the cube (Th' 0, Oh), tetrahedron (T, Td ), and
icosahedron (Y, Y h ). A list of all irreducible subgroups of the group 0(4) is
given in [15]; however, no definite information is available in the literature for
rotation groups of dimension higher than four.
Consider a set of different combinations of OP components of the form
'fJIPl 'fJ2P2 Pl v ,w Ilere PI + P2 + ... + Pl = p. Th e numb er 0 f suc h comb'lila t'Ions
... 'fJlv v
is equal to C~+P_I' For example, for a two-component OP (Iv = 2) we may set
= =
up ct 5 different fourth-order (p 4) combinations: 'fJ[, 'fJi, 'fJr'fJ2, 'fJI'fJ~, 'fJr'fJ~·
Each of these combinations may be viewed as a unit vector of the Cfv+P-I-
dimensional vector space [V/~]. To any set of invariants specified by a group I
we may then assign its own subspace E£
in the space. We denote the dimension
of the subspace Et, that is, the number of invariants of degree p, by Cp(I).
It is evident that one and the same set of invariants of specified degree
may be involved in the IRBI for different I groups; this follows from the IRBI
construction procedure itself, which is based on a step-by-step derivation of
invariants for groups generating a normal series. We call the maximal I group
corresponding to a given set of invariants of degree p, that is, realized in the
subspace Et, a centralizer [15] and denote it by Ip.
The group Ip may be regarded as the stabilizer of the subspace Et. By
decomposing the group O(lv) into cosets relative to the stabilizer Ip , it is pos-
sible to find the decomposition representatives Up and, by operating with these
representatives on the subspace Et, to construct a reducible representation of
the centralizer Ip. The multiplicity factor of the identity representation in-
volved in this representation will then be equal to Cp(I), that is, the number
P
of invariants of degree that generate the subspace E£.
These arguments permit formulation of the major steps in the construction
of invariants that make up thermodynamic potentials. The first step is to find
the vector representation r v for the lv-dimensional rotation group O(lv). From
among all the subgroups of the group 0(1,,), one needs to take as possible 1
groups only irreducible subgroups, that is, subgroups that have an irreducible
vector representation of the rotation group 0(1,,). At the second step it is
necessary to ascertain the constitution of the symmetrized powers of the vector
representation [r v]P' From the group 0(/,,) IR's involved in [r v]P, one has to
pick out those representations the restriction of which on a subgroup 1 contains
an identity representation. The multiplicity factor of the identity representation
gives the number of invariants Cp(I) of degree p for a given 1 group. From all
the 1 groups with the same Cp(I), it is required to choose the maximal group; it
is this group which will be the centralizer r p' Finally, in some way or other (for
example, by the straightforward method) the corresponding set of invariants
may be constructed for each 1p.
This program was implemented in [15] for a four-component OP since the
group 0(4) and its irreducible representations are related to the quaternion
group [18], of which everything is known. An analysis of the symmetrized
powers (p = 2,3,4) of the group 0(4) irreducible vector representation showed
that from all the subgroups it is possible to single out twenty-two centralizers
14 and five centralizers 13 . These sets of invariants exhaust all the cases that
may correspond to some space group four-dimensional IR. Unfortunately, one
cannot tell which of these IR's correspond to the model potentials obtained.
UNIVERSAL CLASSES
As has been established in [16], a total of 106 1 groups exist that are formed
by space group IR's with Lifschitz stars. This means that one and the same
thermodynamic potential should describe a large number of different phase
transitions which may differ from one another in initial symmetry groups and
IR's describing these transitions. Specifically, the transitions may differ in star
numbers and, therefore, in the way the unit cells increase in size.
Invariant characteristics of all such phase transitions are the group 1 and
the number of OP components. We shall say that all the phase transitions that
are described by one potential, that is, that have one 1 group, form a universal
class. The authors of [16] have enumerated all the groups describing phase
transitions of which the initial-phase symmetry may be described by one of the
188 space groups (for ferroelastics). From the tables [16], it is seen that most
of the aforementioned transitions belong to universal classes with the groups
1 = C 4 , C4v , Th, 0, Oh. Therefore it is of practical interest to know all the
IR's involved in each of the above universal classes. Such information enables
124 CHAPTER 4
one, from a knowledge of the relevant IR, to write for a given phase transition
the explicit form of the IRBI and the types of solutions to the equations of
state (mixing coefficient types) and then to calculate the low-symmetry-phase
symmetry groups corresponding to them.
Table 4.1 lists all the three-dimensional IR's leading to each of the five
three-dimensional I groups: T, Th, Td, 0, and Oh. The numbers of IR's in
Table 4.1 are given according to Kovalev and Zak.
Table 4.1
I groups of three-dimensional IR's for cubic and hexagonal space
groups
Lattice rc
X M R
Group
IR I IR I IR I
Tl Tl Zl Th Tl Zl T T4 Z4 Th
T2 Z2 Th T2 Z2 T
T3 Z3 Th T3 Z3 T
T4 Z4 Th T4 Z4 T
Tl Tl Zl Th Tl Zl T T7 Z4 Th
h
T2 Zs Th T2 Zs Th Tg Zg Th
T3 Z2 Th T3 Z2 T
T4 Z6 Th T4 Z6 Th
TS Z3 Th TS Z3 T
T6 Z7 Th T6 Z7 Th
T7 Z4 Th T7 Z4 T
Tg Zg Th Tg Zg Th
T2
h - - - - - - T7 Zg Th
Tg Z4 Th
Table 4.1 continued
Lattice fc
X M R
Group
IR I IR I IR I
Tl
d 7"1 ZI Oh 7"1 ZI Td 7"4 Z4 Oh
7"2 Z2 Oh 7"2 Z2 0 7"s Zs Oh
7"3 Z3 Oh 7"3 Z4 Td
7"4 Z4 Oh 7"4 Z3 0
T4
d 7"1 Z4 0
7"2 Zs Td
- - - - - -
7"3 Z3 0
7"4 Z2 Td
0 1 7"1 ZI Oh 7"1 ZI Td 7"4 Zs Oh

7"2 Z2 Oh 7"2 Z2 0 7"s Z4 Oh
7"3 Z3 Oh 7"3 Z3 0
7"4 Z4 Oh 7"4 Z4 Td
02 7"1 Zs Oh 7"1 Z3 0 7"4 Z4 Oh

7"2 Z4 Oh 7"2 Z2 Td 7"s Zs Oh
7"3 Z3 Oh 7"3 Zs Td
7"4 Z2 Oh 7"4 Z4 0
0h
1 7"1 ZI Oh 7"1 ZI 0 1"7 Z4 Oh
7"2 Z6 Oh 7"2 Z6 Oh 7"s Z9 Oh
7"3 Z2 Oh 7"3 Z2 0 7"9 Zs Oh
7"4 Z7 Oh 7"4 Z7 Oh 7"10 Z10 Oh
7"s Z3 Oh 7"s Z3 0
7"6 Zs Oh 7"6 Zs Oh
7"7 Z4 Oh 7"7 Z4 0
7"s Z9 Oh 7"s Z9 Oh
126 CHAPTER 4
Table 4.1 continued
Lattice rc
X M R
Group
IR I IR I IR I
0 3h 7"1 Z4 0
7"2 Zg Oh
7"3 Z5 Td
7"4 ZlO Oh
- - - 7"5 Z2 Td - - -
7"6 Z7 Oh
7"7 Z3 0
7"8 Z8 Oh
Lattice rfc
X
Group
IR I
T2 7"1 Zl T
7"2 Z2 T
7"3 Z3 T
7"4 Z4 T
r 3
h 7"1 Zl T
7"2 Z5 Th
7"3 Z2 T
7"4 Z6 Th
7"5 Z3 T
7"6 Z7 Th
7"7 Z4 T
7"8 Z8 Th
Table 4.1 continued
Lattice rJc Lattice r Jc

X X
Group Group
IR I IR I
T2
d Tl Zl Td 0 6
h Tl Zs Oh
T2 Z2 0 T2 Z3 Td
T3 Z4 Td T3 Zg Oh
T4 Z3 0 T4 Z4 0
T d5 Tl Z3 0 T5 Z6 Oh
T2 Z5 Td T6 Zl 0
T3 Z4 0 T7 Z7 Oh
T4 Z2 Td TS Z2 Td
0 3 Tl Zl Td
T2 Z2 0
T3 Z3 0 rvc
Lattice
T4 Z4 Td
H
04 Tl Z5 Td Group
IR I
T2 Z4 0 T3 T4 Z4 Th
T3 Z3 0 T4 T4 Z4 Th
T4 Z2 Td
7',5 T7 Z4 Th
h
O~ Tl Zl 0
TS Zs Th
T2 Z6 Oh
T7 T7 Z4 Th
h
T3 Z2 0
TS Zs Th
T4 Z7 Oh
T3 T4 Z4 Oh
d
T5 Z3 0
T5 Z5 Oh
T6 Zs Oh
05 T4 Z5 Oh
T7 Z4 0
T5 Z4 Oh
TS Zg Oh
OS T4 Z5 Oh
T5 Z4 Oh
ogh T7 Z4 Td
TS Zg Oh
Tg Z5 0
TlO ZlO Oh
128 CHAPTER 4
Table 4.1 continued
Lattice rh Lattice rh
M L M L
Group Group
IR I IR I IR I IR I
Sg Tl Zl T Tl Zl Th Cg Tl Zl T - -
T2 Z2 Th T2 Z2 Th C~ T2 Z2 Th - -
D l- 5 Tl Zl Td Tl Zl Oh C66
S
T2 Z2 0 T2 Z2 Oh CJh Tl Zl T Tl Zl Th
CJv Tl Zl Td Tl Zl Oh T2 Z2 Th T2 Z2 Th
C§v T2 Z2 0 T2 Z2 Oh CJh Tl Zl T Tl Zl Th
C~v Tl Zl Td - - T2 Zs Th T2 Zs Th
Civ T2 Z2 0 - - TS Z2 Th TS Z2 Th
DAd Tl Zl Td Tl Zl Oh T4 Z4 Th T4 Z4 Th
D~d T2 Zs Oh T2 Zs Oh Cih Tl Zl T - -
TS Z2 0 TS Z2 Oh T2 Zs Th - -
T4 Z4 Oh T4 Z4 Oh TS Z2 Th - -
D~d Tl Zl Td - - T4 Z4 Th - -
Did T2 Zs Oh - - Dg Tl Zl Td Tl Zl Oh
TS Z2 0 - - T2 Z4 0 T2 Z4 Oh
T4 Z4 Oh - - D4 TS Zs Oh TS Zs Oh
6
Cg Tl Zl T Tl Zl Th D 65 T4 Z2 Oh T4 Z2 Oh
C46 T2 Z2 Th T2 Z2 Th
Ct
Table 4.1 continued
Lattice rh Lattice rh
M L M L
Group Group
IR I IR I IR I IR I
D~ Tl Zl Td - - Dgh Tl Zl Td - - -
D3
6 T2 Z4 0 - - D~h T2 Z3 Oh - - -
T3 Z3 Oh - - T3 Z2 0 - - -
D~ T4 Z2 Oh - - T4 Z4 Oh - - -
CJv Tl Zl Td Tl Zl Oh Dh Tl Zl Td Tl Zl Oh
T2 Z3 0 T2 Z3 Oh T2 Z5 Oh T2 Z5 Oh
T3 Z2 Oh T3 Z2 Oh T3 Z4 0 T3 Z4 Oh
T4 Z4 Oh T4 Z4 Oh T4 Zs Oh T4 Zs Oh
Cgv Tl Zl Td - - - T5 Z3 Oh Ts Z3 Oh
C~v T2 Z3 0 - - - T6 Z7 Oh T6 Z7 Oh
ctv T3 Z2 Oh - - - T7 Z2 Oh T7 Z2 Oh
T4 Z4 Oh - - - TS Z6 Oh TS Z6 Oh
D~h Tl Zl Td Tl Zl Oh D~h Tl Zl Td - - -
D5h T2 Z3 Oh T2 Z3 Oh D~h T2 Z5 Oh - - -
T3 Z2 0 T3 Z2 Oh D: h T3 Z4 0 - - -
T4 Z4 Oh T3 Z4 Oh T4 Zs Oh - - -
Ts Z3 Oh - - -
T6 Z7 Oh - - -
T7 Z2 Oh - - -
TS Z6 Oh - - -
130 CHAPTER 4
References
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2. G.F. Smith, and R.S. Rivlin: Arch. Rational Mech. Anal. 12,93 (1963).
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7. V.D. Kinev, V.E. Naish, and V.N. Syromyatnikov: Fiz. Met. Metalloved.
49, 241 (1980).
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CHAPTER 5
Phase Diagrams in the Space of Thermodynamic

Potential Parameters
15. Theoretical Fundamentals of the Phase Diagram

Construction Method
MAJOR PHYSICAL PRINCIPLES
The thermodynamic potential constructed from order parameter components

transforming by an initial-phase symmetry group IR describes a whole totality
of phase transitions from the initial phase to different dissymmetric phases and
also specifies the phase transitions between these dissymmetric phases. What
kind of phase transition exactly will occur in a given physical system (for a given
IR) depends on the numerical values of the expansion parameters, namely, the
coefficients of second-, third-, fourth- and higher-degree invariants.
Each dissymmetric phase has its individual region of existence in the space
of potential parameters and the character of the phase transition between neigh-
boring dissymmetric phases is determined by the stability conditions for these
phases. To construct a phase diagram means to find the regions of occurrence
of dissymmetric phases in the space of expansion coefficients, to determine the
boundaries between them, and to identify the order of the phase transition on
these boundaries.
In Landau's theory all expansion coefficients are normally assumed to de-
pend weakly on temperature, that is, to be constant for a given crystal, ex-
cept for the coefficient r of the quadratic invariant which changes sign when
the temperature passes through the transition point. Although the expansion
parameters cannot be varied strongly for a given crystal, it is nevertheless of
some interest to construct phase diagrams in the space of these parameters. It
is fundamentally important to ascertain general problems concerning the phase
diagram structure, such as the role of the number of OP components and the
131
132 CHAPTER 5
dependence of phase types on the inclusion into the potential of higher-degree

terms with respect to the op or, put another way, on series break-off effects.
If a general understanding of these problems is gained, it is probably hardly
necessary to establish the complete structure of the phase diagram in each
particular case.
The situation is different when the system is subject to some physical field
X. The effect ofthis field manifests itself, on the one hand, in the X dependence
of the expansion parameters, primarily the parameter r, and, on the other, in
the occurrence of op- and X-dependent terms in the thermodynamic potential
itself. In this case it becomes possible to study phase transitions in terms of the
variables (T, X) (X may be a multicomponent quantity). In this formulation of
the problem, the phase diagram should be studied in the space of the variables
T and X varying in experiment, and all the potential expansion coefficients,
starting with the terms proportional to 1]3 and 1]4, should be viewed as fixed.
An analysis of the phase transition in such a statement of the problem will be
considered in Chap. 7. In this chapter we focus on phase transitions in the
absence of an external field.
Mathematically, the problem of constructing a phase diagram reduces to
one of bringing out all the minima of a function of several variables, namely,
the thermodynamic potential ~:
(15.1)
Here ~n(1]).) is a polynomial of degree n in the variables 1]).. As a rule, the 1]).
are chosen as the op components.
In keeping with the Landau theory, one begins the construction of the
phase diagram by finding all the extrema of the potential ~, that is, by solving
a system of non-linear equations
a~ = 0, (\,,= 1, 2, ... ,I v ) ,
JOl (15.2)
v1]).
where Iv is the dimension of the relevant IR. The subsequent analysis is broken
up into several stages.
At the first stage one finds the types of solutions to equations (15.2). Each
solution type is specified by the number of non-zero 1]). components and by the
ratios between these. As shown in Chap. 3, all the solution types possible,
that is, all mode mixing types, are found from group-theoretic considerations,
each solution type corresponding to a low-symmetry phase of its own. The
DIAGRAMS IN THERMODYNAMIC PARAMETER SPACE 133
dependence of the non-zero components 1]>. on the coefficients contained in the

potential is found at the second stage. To this end, one has to solve the
equations of state resulting from the general equations (15.2) on substituting
into these a particular prescribed-symmetry solution type.
A further step in the construction of a phase diagram is to disclose those
solutions to the equations 01 state that conel>\'Ic)\\G. to a yffi:n\.TI\\Yffi. 0\ \,\\~ \'I\)-
tentiaJ . This cal1s for setting up the determinant of second-order derivatives
of the potential with respect to the components 1]>.. On inserting there the
solutions to equations (15.2) and requiring that all principal minors be positive
definite:
118:::1]1' II ~ 0, (A, p, = 1,2, ... ,Iv), (15.3)
one can find the ratios between the coefficients of the potential at which a
given solution corresponds to a minimum. The equality sign in equation (15.3)
gives the expression for the stability boundary of the phase investigated.
The final stage in the construction of the phase diagram is to explore the
positive definiteness of the potential. Analysis of the first- and second-order
derivatives of the potential with respect to the parameters 1]>. provides informa-
tion about the behavior of in the vicinity of local extrema as a function of the
values of the phenomenological coefficients involved in the expression (15.1);
in this case the behavior of the potential in the other regions of the space
of the variables remains undefined. Two possibilities can evidently be singled
out. One of them is that the value of the potential increases continuously
when the parameters 1]>. enhance along any direction in the multidimensional
space of the OP 11 = {1]>.}. In this case the local minima found from the condi-
tions (15.2) and (15.3) describe the stable states of the system into which the
latter may pass as a result of a phase transition. The other possibility is that
at certain values of the coefficients of the potential the becomes negative at
least in one of the directions in the space of the parameters 1]>. and increases in
magnitude with 1]>.. In this case the local minima describe metastable states; in
constructing the phase diagram in the space of phenomenological coefficients, it
is therefore necessary, in terms of the potential model (15.1) chosen, to isolate
the region of positive definiteness of the potential in which the local minima
describe stable states. When it is desired to explore a potential with values of
coefficients at which the condition of positive definiteness is violated, one has
to allow for the expansion terms that follow next in the series (15.1).
We now formulate the scheme of testing the thermodynamic potential
(15.1) for positive definiteness. The behavior of at large values of the para-
134 CHAPTER 5
meters 7]>. is evidently determined by the highest-degree term n(7]>.) in the

model adopted. It is convenient to pass on to new variables 7]~. To this end,
we set 7]>. = R7]~, where R2 = 2:>. 7]~ and the quantities 7]~ satisfy the condition
"'"'
~7] 12 >. -- 1. (15.4)
>.
The quantity n (7]>.) then goes over into Rnn (7]D and the condition of positive
definiteness for n(7]>.) reduces to the requirement that the quantity n(7]~) be
positive definite on the multidimensional sphere of unit radius prescribed by
equation (15.4). The quantity n (7]D will be positive definite if it is positive at
the points of the minimum on the sphere (15.4). These points are found from
the equations
~~ = 0, n = n(7]~) + Jj (2: 7]~ - 1), (15.5)
7]>. >.
Jj being an undetermined Lagrangian multiplier. The coordinates of the ex-
°
trema 7]~o found from equations (15.5) are substituted into n, and it is re-
quired to fulfill the condition <pn(7]~o) > which results in inequalities for the
coefficients involved in n(7]~o).
REQUISITE THEOREMS FROM THE ALGEBRA OF POLYNOMIALS
The stages enumerated above are initial steps for the construction of the phase
diagram itself. The biggest task is to determine the stability boundaries of the
phases. To this end, it is necessary to simultaneously solve equations (15.3)
(in the case of the equality sign) with the equations of state (15.2). Practical
methods for performing such phase diagram analysis have been developed by
Gufan et al. [1-3]. These methods are based on the use of well-known concepts
in polynomial algebra.
From a mathematical viewpoint, the problem reduces to one of finding the
common roots of the polynomials
I(x) = aoxnn + arx n- 1 + ... + an-lx + an,

(15.6)
g(x) = box' + b1x·- 1 + ... + b._1x + b.,
(ao f:. 0, bo f:. 0). As the polynomial I(x) one may take the equality to zero
of one of the principal minors (15.3), the equation of state playing the role
of the polynomial g(x). From the algebra of polynomials [4], it follows that
two polynomials I(x) and g(x) have common roots if and only if the resultant
R(J,g) of these polynomials is equal to zero. By the resultant R(J,g) we mean

the determinant
ao al ... an 0 0 ... 0
R(J,g) = 0
0 ao
0 ... 0
al ., .an
ao
0 ... 0
al ... an
} s lines
(15.7)
bo bi .. , b. 0 0 ... 0
0 bo bi ... b. 0 ... 0 } n lin"
0 0 ... 0 bo bi ... b.
The equation R(J, g) = 0 defines the stability boundary of a given phase in the
space of potential parameters. A further step is to find the phase transition
'lines' (surfaces). In those cases where the regions of stability of two neigh-
boring phases do not overlap, the stability boundary delimiting these phases
is the boundary of second-order phase transitions. But if there is a region
in which two or more phases coexist, a first-order phase transition boundary,
determined from the condition that the energies of those phases be equal in
magnitude, should pass in that region. The problem of finding first-order phase
transition 'lines' is solved in similar fashion to that of finding stability lines.
The polynomial f( x) in this case is determined from the equality of the poten-
tials of the neighboring phases.
Let it be noted that in analyzing phases described by more than one com-
ponent of the multicomponent OP, the number of equations of state is equal
to the number of non-zero OP components. In this case the stability lines and
the phase transition lines are found by successively calculating the necessary
number of resultants.
When finding stability lines and phase transition lines, one should allow for
the fact that the requirements that the principal minors be equal to zero and
the energies of the phases be equal in magnitude are fulfilled for all solutions
to the equations of state, including those corresponding to a maximum of the
potential as well as those corresponding to imaginary OP values. To single out
non-physical solutions, it is therefore reasonable to analyze the distribution
of the roots to equations of state in the space of thermodynamic-potential
coefficients, which permits one to isolate the regions of existence of real-valued
solutions.
The problem of the distribution of solutions to equations of state is solved
with the help of the Descartes rule [4].
1. The number of positive roots of a polynomial f( x) with real coefficients
136 CHAPTER 5
either is equal to the number of sign reversals in the series of coefficients I(x)
or is an even number less.
2. The number of negative roots is equal to the number of sign reversals
in the series of polynomial coefficients I( -x) or is an even number less.
Additional information about the distribution of roots to equations of state
may be derived from an analysis of the discriminant of the polynomial in ques-
tion [4]. The discriminant D(J) of the polynomial I(x) = aoxn + alx n - 1 +
... + an-1X + an is related to the resultant of the polynomial I(x) and to its
derivative I' (x) by the formula
R(J,J') = (_1)n(n-l)/2 ao D(J). (15.8)
If I(x) is a polynomial with real-valued coefficients and has no multiple
roots, then D(J) > 0 if the number of pairs of conjugate complex roots I( x) is
even. D(J) < 0 in the case of an odd number of conjugate complex roots.
In the subsequent sections of this chapter it will be shown in what fashion
these concepts can be exploited in a practical analysis of phase diagrams [3].
Despite the progress made using the theorems of polynomial algebra cited
above, the problem of constructing a phase diagram in the case of a tran-
sition over a multicomponent OP and with allowance for sixth-degree and
higher-order invariants in the thermodynamic potential expansion (15.1) in-
volves considerable technical difficulties. One of these difficulties is the neces-
sity to calculate literal determinants (resultants) of high order. Substantial
difficulties are encountered also in analyzing expressions for the phase transi-
tion lines and stability lines that are obtained by calculating such resultants.
The large number of phenomenological variables (coefficients in the thermody-
namic potential), which augments dramatically with increase in the degree of
the invariants allowed for in the potential and in the case of a multi compo-
nent OP, leads to a substantial increase of the various phase diagram versions.
Each version corresponds to a particular cross-section of the multidimensional
space of thermodynamic-potential coefficients in which the phase diagram is
constructed. That is to say, each version is characterized by a certain ratio of
these coefficients.
It might be well to point out that the above difficulties may be negotiated
by means of a computer. Problems of computer processing of high-degree
polynomials have been considered in the monograph [3], where all the problems
of polynomial algebra are treated on the basis of the concept of the innor
introduced by the author. Computer processing of resultants is employed also
in [5,6].
16. The One-Component Order Parameter
THE FORM OF THE THERMODYNAMIC POTENTIAL
We begin the construction of phase diagrams with the simplest case of a one-
component OP, assuming the thermodynamic potential to contain only even
degrees in the expansion:
(16.1)
It is of interest to analyze such a potential in detail as there are numerous

phase transitions that occur through a one-dimensional representation. Apart
from this, the results obtained for such a potential may be used to analyze
complicated potentials with multicomponent OP's. Indeed, among the various
types of solution, for example in the problem with the three-component OP
{7]1, 7]2,7]3}, there arise solutions of the type (7] 0 0), (7] 7] 0), (7] 7] 7]) that are
characterized solely by the quantity 7]. The analysis of the equations of state,
stability lines, and phase transition lines for these types of solution may be
reduced to the problem (16.1) to within the transcriptions of the coefficients.
One of the main goals of the present section is to ascertain what changes
the phase diagram undergoes when high-degree terms are successively added
to the potential. The case of the potential containing only two first terms (the
7]4 model) was examined in detail in §l. The 7]4 model describes a second-order
phase transition that occurs along the phase transition line r = o. The OP in
the low-symmetry phase is determined by the expression
(16.2)
giving a temperature dependence of 7] that is typical of the second-order phase

transition (Fig.1.2).
THE 7]6 MODEL
The following model contains a sixth degree in the expansion of in 7]:
(16.3)
For the potential (16.3) to be positive at large values of 1171, the following
inequality should be fulfilled: v > 0; the coefficient u may in this case be of
arbitrary sign. The equation of state
(16.4)
138 CHAPTER 5
r r
7/-0 71=0
... lJ. LL
71, 711
(a)
II III (b)
Fig. 5.1. Stability regions of solutions: ( a) rJi and (b) 1}~ for the 1}6
model.
has the solution
2
1}1 = - -u+u
-3v g1 r v
- -2, (16.5)
3v u
1}~ = -~
3v
- ~J1-
3v
3rv.
u2
(16.6)
Allowing for the equation of state (16.4), the stability condition 8 2q,j81}2 > °
for these solutions may be written in the form
r + U1}2 < 0. (16.7)
Account must be taken also of the conditions under which the solutions (16.5)
and (16.6) are real. One of these conditions is
1 - 3rv >
u2 '
° (16.8)
while the others are formulated separately for each of the solutions, 1}I and 1}~:
u > 0, r < °
or u < 0, r> ° and u < 0. (16.9)
Simultaneous use of the stability conditions (16.7) and the reality conditions
(16.8) and (16.9) leads to the inequalities
u> 0, r < 0, (16.10)

defining the domain of existence of the solution 1}f, and to the inequalities
u2
u < 0, r < 3v' (16.11)
defining the domain of the solution 1}~. The stability regions ofthe real solutions
1}f and 1}~ are sketched in Fig. 5.1. The stability region of the initial phase
1} = °
is defined by the inequality r > 0.
Finally, to construct the phase diagram, we find the phase transition lines.
From the condition <1>(1]) = 0 (equality of the energies in the phases with 1] ::P 0
and 1] = 0) and allowing for the equation of state, we obtain
(16.12)
The solution of this equation, 1]2 = 0, defines the line of second-order phase
transitions, r = O. As follows from the form of the solutions (16.5) and (16.6),
the condition 1]2 = 0 is satisfied only by one solution, namely 1]f. It is this
solution that describes the OP change at the second-order phase transition.
A similar conclusion may be drawn directly from an analysis of the stability
conditions for the solution 1]r. As can be seen from Fig. 5.1( a), the stability
region of the initial phase 1] = 0 and that of the low-symmetry phase 1]f do not
overlap, but they have a boundary in common; it is this boundary which is the
second-order phase transition line.
One more equation results from equation (16.12):
2r+ U1]2 = O. (16.13)
The expression (16.13) specifies the line of the first-order phase transition to
the phase described by the solution 1]~ (Fig. 5.1(b)). This line will be obtained
by substituting into equation (16.13) the expression (16.6) for 1]~:
U2
r=-. (16.14)
4v
The OP jump on the phase transition line (16.14) is
2r 2r
1] = - -; = - 4v . (16.15)
In final form, the phase diagram for the potential (16.3) is sketched in
Fig. 5.2. Thus the 1]6 model turns out to lead to an extension of the domain
of existence of dissymmetric phases on the (r, u) plane. With negative u a
new phase arises, the transition to this phase being of the first kind. With all
positive u the phase transition remains a second-order transition, just as in the
1]4 model.
THE 1]8 MODEL
Let us consider the consequences of allowing for the next following term of
degree eight in the potential expansion. This problem is an example of
140 CHAPTER 5
"
'1"'0
I
Fig. 5.2. Phase diagram for the 7]6 model with a one-component order
parameter.
applying Gufan's phase diagram construction method in practice. From the

requirement that the potential be positive for large values of the OP 7], it
follows that w > 0, where w is the coefficient of the eighth-order invariant.
Subject to this condition, the coefficient v may be of arbitrary sign. We start
by considering the case v < O.
In this model the equations of state
(16.16)
are cubic for the quantity 7]2. Following the standard procedure of constructing
phase diagrams, we could write out the solutions of this equation in general
form and then use these to analyze the conditions under which the phases are
stable and their energies are equal. Technically, however, this procedure turns
out to be very complicated. Therefore, as proposed in §15 [3], we begin the
construction of the phase diagram by analyzing the number of roots of the
equation of state in the space of the coefficients r, u, v, and w.
Figure 5.3 presents the distribution of the roots to equation (16.16) in the
plane of the variables rand u for the case v < 0 in keeping with the Descartes
rule. The notation (2,0)+ 1- implies that in the corresponding region of the
parameters rand u the equation of state has either two positive solutions for
7]2 or none and one negative root.
More complete information on the distribution of the roots of equation
(16.16) may be obtained by examining its discriminant. To this end, we rear-
range equation (16.16) in the form
y3 + 3py + 2q = 0, (16.17)
2 U
Y= 1] + -,
V
3p = - ,
4w
2w
r 2vu _ 3v 2
2q = 4w - (4w)2' u = u - 8w' (16.18)
"
Fig. 5.3. Distribution of roots to equation (16.16) for the model on

the (r,u) plane.
On substituting the expressions (16.18), the discriminant curve
becomes
f = ~u ±
2w
(_8_)
27w
1/2 (_U)3/2 (16.19)
The discriminant curve is shown in Fig. 5.4 (dot-and-dash line). The coordi-
nates of the points through which the discriminant curve passes are as follows:
(16.20)
The coordinate U c can be found by solving the cubic equation that results from
equation (16.19) by substituting into the latter the expression rc = O.
Availing ourselves of the familiar fact that in the case of D > 0 the cubic
equation has one real root and two conjugate roots, and for D < 0 three
different real roots, we are in a position to refine the picture as to how the
roots to the equation of state are distributed on the (r, u) plane (Fig. 5.4).
The 0 [{ line may be disregarded as this is the line of concurrence of two
negative roots for TJ2 and corresponds to imaginary values of the OP TJ.
142 CHAPTER 5
r
\. let
(2,+r) B
(n
\ I
])<0 ]»0
\
\c IJ LI
0 ---Q .
/-/---- -, .Y
/
/if (1+) /) "A
~
(f+)
]) >0 (3
Fig. 5.4. Distribution of roots to the equation of state (16.16) and

the discriminant curve [3].
Note that in more complicated cases it is more convenient to calculate

the discriminant according to the formula (15.6) and the resultants involved in
equation (15.6) can be computed in literal form with the help of a computer
[3] .
We now analyze the stability condition o2if!j01]2 > O. On the boundary of
the stability region we have the equation
(16.21)
Using the equation of state (16.16), the expression (16.21) may be rearranged
to read
(16.22)
The stability boundary is given by the system of two equations (16.22) and
(16.16). The condition for this system to be solvable is, as shown in §15, that
the resultant be equal to zero:
r 2u 3v 4w 0
0 r 2u 3v 4w
R= u 3v 6w 0 0 =0 (16.23)
0 u 3v 6w 0
0 0 u 3v 6w
It is easy to see that the stability boundary determined by equation (16.23)

coincides with the discriminant curve (16.19). Indeed, the discriminant curve
D = 0 can be obtained by equating to zero the resultant of the equation of

state and by equating to zero its derivative with respect to the OP TJ. Since
the derivative of the equation of state coincides with equation (16.22), the
resultant involved in the formula (15.6) for the discriminant curve similarly
coincides with equation (16.23).
(a) (b) (c)
tial for three regions corresponding to the sections

and 6-(J' (c).
a,
Fig. 5.5. Order parameter dependence of the thermodynamic poten-
(a), ,-6 (b),
Let us see what changes the states of the system undergo along the a{3,6(J'
line (Fig. 5.4). On the a - , segment the equation of state has one real root
and the thermodynamic potential has the shape characteristic of the TJ4 model
(Fig.5.5a). At the point, two more positive solutions arise on TJ2; the TJ depen-
dence of is depicted in Fig.5.5b. In the region OAGO (Fig. 5.4) a first-order
phase transition is possible between the phases which is described by different
solutions of the equation of state (TJ1 and TJ3)' This is an isostructural phase
transition with the temperature dependence of the OP, shown (schematically)
in Fig. 5.6 [7]. Finally, in the region 8 - (J' the system again has one solution.
T
o
Fig. 5.6. Variation of the order parameter at the isostructural phase

transition corresponding to Fig. 5.5b.
144 CHAPTER 5
We will consider in addition those spatial regions (r, u) where two positive
solutions of the equation of state for ",2 exist. The corresponding potential is
portrayed in Fig. 5.5c. These regions, as is seen from Fig. 5.4, overlap with
the stability region of the initial phase", = 0, so the phase transition from the
initial phase to the low-symmetry phase in these regions will be a first-order
transition. As can be seen from Fig. 5.5a, a second-order phase transition
in the ",8 model is possible; the second-order phase transition line originates
at the point C and is described by the equation r = 0 (the boundary where
the stability regions of the initial and low-symmetry phases touch). The final
form of the phase diagram is shown in Fig. 5.7, where the dot-and-dash lines
indicate the stability boundaries of the phases (Fig. 5.4), the solid line is the
line of first-order phase transitions, and the dashed line is the line of second-
order phase transitions. On the ED line and its continuation to the left a phase
transition from the initial phase occurs, while on the EA line an isostructural
phase transition takes place.
Fig. 5.7. Phase diagram for the ",8 model with a one-component order
parameter [7].
Next we find the explicit form of the equations for the line of the phase
transitions depicted in Fig. 5.7. The AE line, corresponding to an isostructural
phase transition, is found from the condition that the minima of the potential
cI> sketched in Fig. 5.5b be equal in magnitude:
(16.24)
and is determined by the equation
V v3
r= - u - - - . (16.25)
2w 8w 2
The ED Line (and its continuation to the left) is found from the condition that
the energy of the initial phase be equal to that of the dissymmetric phase
cI>(7]) =0 (16.26)
allowing for the equation of state (16.16). The ED line is determined by the
equation
r* = C:)u* + (2:W) (-u*) 1/2 3/2 (16.27)
with r* = r - v /27w u* = v /3w. The points

3 2, U - 2 E and D have the
= =
coordinates 1'E 0, UE v /4w and rD
2 =
-4v /27w , UD O.
3 2 =
The phase diagram analysis performed above applies to the case 'Y < O. A
complete phase diagram is sketched in Fig. 5.8. The triangular surface AEO
at the bottom of Fig. 5.8 is the boundary of isostructural phase transitions
(Fig. 5.7). No isostructural transitions occur in the region v > 0 and the phase
diagram in it has the same shape as that in the 7]6 model.
r
v
Fig. 5.8. Phase diagram in the space of the parameters (1', u, v) for
the 7]8 model in the case of a one-component order parameter.
Thus an analysis of the phase diagrams in the three consecutive models

differing in the addition of a higher-degree term with respect to 7] in the po-
tentialleads to the following sequence of results. The 7]4 model describes only
a second-order phase transition (Fig.1.4). The 7]6 model permits description of
a first-order phase transition to a low-symmetry phase (Fig. 5.2). The next
model, 7]8, enables one for the first time to describe an isostructural phase
transition (Fig. 5.7). It is important to note that these new phenomena in the
picture of phase transitions, arising from the addition of a higher-order term to
146 CHAPTER 5
cl>, occur only for negative coefficients in the highest degree with respect to 17
in the initial model. Addition of higher degrees with respect to 17 does not lead
to qualitatively novel phase transition types, but only increases the number of
isostructural transitions [7].
SUCCESSION OF SOLUTIONS TO EQUATIONS OF STATE
The succession of solutions to equations of state in the case when a new degree
17 4 is added to the thermodynamic potential has been investigated in general
form by Aizu [8]. For convenience in reasoning, we transcribe the potential
(16.1) as
(16.28)
We denote the various solutions to the equation of state ocl>/OTJ = ° as
(16.29)
and consider one of the solutions Ii (Cl, C2, ... ). Following Aizu, we will call the
function J;( Cl, C2, ... ) an n - s type function if the following two conditions are
fulfilled:
1. The function J;(Cl, ... ,Cn,Cn+l,O, ... ,O) is finite (different from zero)
at finite values of the coefficients Cl, ... , Cn+l and c" = 0, where K > n + 1.
2. °
lim Cn+di (Cl, ... , Cn , Cn+l, 0, ... , 0) "¥= at arbitrary values of the
C n +l -+0
coefficients Cl, ... , cn .
Assume also that all coefficients c,,' except the coefficient Cl, are temper-
ature independent and Cl ,...., (T - Tc).
To elucidate the meaning of the concept introduced, we determine to what
type the two solutions of the equation of state which we had in the 17 6 model
belong. In the new notation these solutions (16.5) and (16.6) have the form
(16.30)
(16.31 )
To start with, consider the solution !1(Cl, C2, C3). Assuming that C3 -+ 0,
expand equation (16.30) in a series of C3:
(16.32)
From this expression, we obtain two equations,
(16.33)
(16.34)
which show the solution (16.30) to be of the 1 - s type.

In order to determine the kind of the phase transition to the state described
by the 1 - s function f(cl, C2, C3), we find the value of this function at Cl = 0:
(16.35)
Thus the value of the OP at the phase transition point is equal to zero, so the
1 - s function (16.30) describes a second-order phase transition.
Consider the second solution (16.31). Evidently,
(16.36)
Allowing for the fact that the function h(cl, C2, C3) is finite at finite values of
the coefficients Cl,C2 and C3, we infer that h(cl,c2,c3) pertains to the 2 - s
type. We find the kind of phase transition described by the 2 - s function
f2(cl,c2,c3). Since
(16.37)
we conclude that the second solution to the equation of state, (16.31), which
is a 2 - s function, describes a first-order phase transition.
These results may be generalized and formulated in the form of the state-
ment that all equation of state solutions of n - s type with n > 1 describe
first-order phase transitions, while a solution of 1 - s type describes a second-
order phase transition. Thus, if there is an explicit form of the solutions to
the equation of state in the TJ2n model, it is easy to draw a conclusion as to
the kind of the phase transition to the state described by each solution. It is
noteworthy that while only a 1- s-type solution corresponds to a second-order
phase transition, the solution types corresponding to first-order transitions are
2 - s, 3 - s, etc. The superscript n may serve as a classificational index among
the various first-order phase transitions in a given system [8]. By adding new
terms to the thermodynamic potential, we shall naturally obtain new types
of solution to the equation of state, which correspond to higher values of n.
148 CHAPTER 5
Conversely, the breaking of a series for CP leads to the loss of some solutions of
the corresponding n - s type which describe first-order transitions.
On returning to the initial notations, C1 = r, C2 = U, C3 = v, etc., of the
thermodynamic potential (16.1) and comparing the expression (16.33) with the
solution (16.2) in the "14 model, we see that the solution (16.5) to the equation
of state in the "1 6 model derives from the unique solution (16.2) to the equation
of state for the preceding "14 model. As for the solution (16.6), it is qualitatively
new and is due entirely to allowance for the higher degree in the expansion of
the potential in the OP "1.
17. The Two-Component Order Parameter
THE "14 MODEL
We will study the features peculiar to phase transitions due to the 2-component
order parameter by the example of systems characterized by a potential of the
form
(17.1)
This is the simplest and at the same time a sufficiently general potential that
may arise in the description of a phase transition going over the two-dimensional
representation of a large number of space groups specifying the initial phase.
By contrast with the one-component OP, it is not one but several dis-
symmetric phases differing in symmetry that may arise in the situation under
consideration. These phases correspond to different solutions of the equations
of state arising in the potential minimization process. For the potential (17.1)
there will be two such equations:
As was described in detail in Chap.3, there are different types of mixing

coefficients of responsible-IR basis functions corresponding to the possible dis-
symmetric phases. Since it is the mixing coefficients that are order parameters,
the symmetry of the phases is determined by the type of solution ("11"12) of
the minimization equations. In our example there may occur, in addition to
the initial phase with "11 = "12 = 0, three dissymmetric phases, which we will
prescribe by three types of solutions:
1. ("10), 2. ("1"1), 3. ("11"12). (17.3)

(The symbol ('T)l 'T)2) denotes that 'T)l :j; 'T)2 :j; 0.) The initial phase will be denoted
by 0. It is, however, a simple matter to see that the system of equations (17.2)
has no solution of the type ('T)1'T)2). Indeed, on setting up the difference of the
equations (17.2) (having preliminarily reduced the equations by the factors 'T)l
and 'T)2), we obtain the equation (2Ul - U2) (17f - 1]D = 0, which is satisfied
only if 'T)f = 'T)~. Thus only solutions of the first and second types enumerated
in equation (17.3) are possible at arbitrary Ul and U2.
Consider phase 1. The equations of state reduce to one:
(17.4)
whence we find 'T)2 -1' /2Ul, so that the OP is real subject to one of the
conditions:
l' < 0, Ul < ° or l' < 0, Ul > 0. (17.5)
We find the stability region of phase 1. To this end, we calculate the
second-order derivatives of the potential (17.1):
([>'7l'71 = 2(1' + 6Ul'T)r + U2'T)n,

([>1/11/2 = ([>1/21/1 = 4U21]1'T)2, (17.6)
([>1/21/2 = 2(1' + 6Ul'T)~ + U21]i).
On substituting into equation (17.6) the solution 'T)1 = 'T), 'T)2 = 0, we write the
stability condition (see equation (15.3»:
(17.7)
from which the two inequalities follow:
If we substitute here the expression for 1]2, determined from the equation of
state (17.4), then these inequalities may be reduced to the following two in-
equalities:
1':::; 0, (17.8)
The set of stability (17.8) and reality (17.5) conditions yields the ultimate
result: Phase 1 has a region of stability of real solutions which is given by the
inequalities (Fig. 5.9)
(17.9)
150 CHAPTER 5
Phase I
P hQ.se 2
Fig. 5.9. Phase diagram for the.,,4 model with a two-component order
parameter. 1, local-stability lines of phases; 2, positive-definiteness
lines of the potential <II.
Consider phase 2, which is characterized by the solution type (.".,,). In this

case too, the equations of state (17.2) reduce to one equation:
(17.10)
The stability condition
(17.11)
reduces to two inequalities:
(17.12)
The condition for the solution of the equation of state (17.10) to be real has
the form
r > 0, 2Ul + U2 < 0 or r < 0, 2Ul + U2 > o. (17.13)
Finally, the stability region of real solutions for phase 2 is restricted by the
inequalities (Fig. 5.9)
(17.14)
Completing the construction of the phase diagram, let us see what ad-
ditional constraints may be placed on the phase stability region by the re-
quirement that the potential (17.1) be positively definite. In keeping with
the recommendations of §15, the positive definiteness of the potential (17.1) is

determined by the positive definiteness of the quartic form <1>4:
"'4
iF.
= U1 R4(-4+-4)+
"11 rl2 U2 R4(-2-2)
"71 "72 .
In turn, the requirement that <1>4 be positive definite reduces to exploring the
sign of <1>4 at the points of the minimum on the circle of unit radius r;r +
r;~ = 1 (§15). These minima are found from the condition fJ4/fJ"7i = 0,
where <l>4(/-l) = <1>4 + /-l(r;r + r;~ - 1). The equations have three solutions:
(r;lo 0), (0 r;20) , (r;lo, ±r;2o). We substitute each of the solutions into <1>4. In
=
the case of (r;lo 0) or (0 r;2o) type solutions, /-l -2U1R2, r;~o =1, <l>4(r;>.o) =
R4u1. From the condition <l>4(/-l) > 0, we find that the coefficient U1 should be
positive, U1 > O. The solution (r;10, ±r;20) yields <1>4 (r;10 , ±r;20) = ~R4(2u1 +U2),
whence we find the second inequality: 2U1 + U2 > O. Thus the set of inequalities
U1 > 0,2U1 + U2 > 0 determines the region of positive definiteness of the
potential (17.1). This region is singled out in Fig. 5.9 by a double dot-and-
dash line. Thus the region of positive definiteness of in this example does
not change the regions of existence of phases obtained from the local-stability
conditions. On the (ru2) plane the regions of stability of both dissymmetric
phases are shown in Fig. 5.10.
-2uI
1
l' hQ.se 2
2uI
Phose I
... z
U
Fig. 5.10. Stability regions of the phases in the "7 4 model in the (r, U2)
plane.
The "7 4 model, as is seen from the results obtained, does not describe the
transition between phases 1 and 2. Indeed, phases 1 and 2 have a common plane
2U1 - U2 = 0 on which the stability conditions for these phases are violated.
The phase transition line 1 f-+ 2 may be expected to lie in this plane. This line
should be found from the condition for the potentials of the two phases to be
equal: <1>("71 = "7, "72 = 0) = <1>("71 = "7, "72 = "7). On substituting the solutions of
the equations of state (17.4) and (17.10), the condition for the potentials to be
152 CHAPTER 5
equal becomes
r( 2U l - U2) _ 0
4U1(2u1 + U2) - .
This equation does not give us an expression for the transition line, that is, the
relation of the temperature-dependent coefficient r to the other parameters, U1
and U2. The problem whether a phase transition is possible between phases 1
and 2 can be solved only by going beyond the framework of the 1J4 model, that
is, by adding higher-order terms to the potential.
THE 17 6 MODEL
In the potential (17.1) we now take into account the sixth-order terms, which
we represent as (l7f + 1J~? and (l7f + l7n1Jfl7~' This form is equivalent to the
assumption that the IRBI for the potential contains only two invariants: l7f+l7~
and l7fl7~' Note also that the fourth-order term l7t + l7i in equation (17.1) may
be expressed in terms of the same two invariants. We can largely simplify the
intermediate calculations and bring the phase diagram into a more symmetric
form if we rewrite the resulting expression for in equivalent form:
 = r(l7r + 1J~) + U1(l7r + 1JD 2 + U2[(l7r -1JD2 - 417rl7~1+

+vl(l7i + 17~)3 + v2(l7i + l7~)[(l7i -17~? - 417il7~1· (17.15)
To analyze similar expressions that are symmetric with respect to the substi-
tu tion 171 f-+ 172, it is convenient to introduce the trigonometric variables
171 = 17 cos ¢, 172 = 17 sin ¢, (17.16)
in terms of which is expressed as follows:
(17.17)
The requirement that the potentials (17.15) and (17.17) be positive definite
leads to constraints on the values of the coefficients V1 and V2: V1 > 0, -V1 <
V2 < V1'
We begin the construction of the phase diagram by analyzing the equations
of state
(17.18)
(17.19)
From the second equation of state, (17.19), it follows that either sin 4¢ = 0
or U2 + V2"1 2 = O. The case sin 4¢ = 0 refers to two phases:
cos4¢ = +1, "1 =1= 0 (phase 1+), cos4¢ = -1,"1 =1= 0 (phase 1-), (17.20)
while the case U2 + V2"1 2 = 0 corresponds to one phase:
sin 4¢ =1= 0, "1 =1= 0 (phase 2). (17.21)
We start by exploring phase 2. As is seen from equations (17.18) and

(17.19), adding invariants of degree six to the thermodynamic potential allows
us to obtain for the first time a low-symmetry solution of general type. Indeed,
equations (17.18) and (17.19) have the solutions
(17.22)
which correspond to phase 2. The stability condition
(17.23)
reduces to the inequality "1 6 sin 2 4¢ < 0, which does not hold with real "1. Thus
phase 2 has no stability region in the "1 6 model. Phase 2 will occur for the first
time in the phase diagram only in the successive "1 8 model.
Consider now phases 1+ and 1-. The equations of state reduce to one
equation,
(17.24)
where U = Ul ± U2, V = Vl ± V2; the ± signs refer to phases 1+ and 1-

respectively. The stability condition (17.23) for each of the phases consists of
two inequalities:
(17.25)
The equation of state (17.24) coincides, up to the replacement of the vari-

ables, with equation (16.4) for the one-component OP, therefore we can use the
phase diagram analysis results for the one-component OP. The phase diagram
will be plotted in terms of the variables rand U2' The coefficient U2 belongs to
an anisotropic invariant of degree four and one should expect that its sign and
value may largely affect the phase transitions that occur in the system. Shown
154 CHAPTER 5
Fig. 5.11. Stability regions of the phases for the 1]6 model in the
(r,u2) plane.
by a dot-and-dash line in Fig. 5.11 are the stability lines of phases 1+ and 1-,
obtained from the first stability condition (for the case Ul > 0).
The stability region of phase 1+ is determined by the inequalities
(17.26)
For phase 1- ,
Ul - U2 > 0, r < 0; (17.27)
We find the stability boundary corresponding to the second condition

(17.25) by requiring that the left-hand side be equal to zero. Expressing the
value of 1}2 from the equality obtained and substituting this value into the
equation of state (17.24) yields the stability line:
(17.28)
In Fig. 5.11 these lines are indicated by a double dot-and-dash line for the case
V2 < O. Inspection of this figure shows that phases 1+ and 1- have a region
of overlap through which a first-order phase transition line 1+ +-+ 1- should
pass. The final form of the phase diagram is given in Fig. 5.12. As can be
readily seen, the expressions for the first-order phase transition lines 0 +-+ 1+
and 0 +-+ 1- coincide, up to the replacement of the variables, with the case of
the one-component OP:
Ul ± U2
(17.29)
r= 3(Vl±V2)'
Fig. 5.12. Phase diagram for the 17 6 model in the (r, U2) plane.
The first-order phase transition line 1+ ...... 1- may be found from the
condition <1>(17+) = <1>(17-) which is easy to reduce to the form
(17.30)
By substituting into this expression the solutions of the equations of state

(17.24) we can, in principle, find the equation for the phase transition line.
However, as the corresponding expression is very cumbersome in form, it is not
worth while quoting it here. A jump of the OP on the phase transition line
(17.30) in the form of the expression for (17~ - 17:') may be obtained also from
equation (17.30) by substituting there the (17+ ± 17~) found from the explicit
form of the solutions to equations (17.24). In the more complicated cases where
the solutions to the equations of state cannot be written out in explicit form, the
procedure of finding phase transition lines reduces to a successive calculation
of several resultants.
From the analysis performed above, it is seen that both in the case of a one-
component OP and in that of a two-component OP allowance for sixth-degree
invariants leads to the same phase diagram transformation: First-order phase
transition lines occur between the initial and the low-symmetry phase. As has
been shown in [7], addition of eighth-degree invariants to the potential (17.15),
just as in the one-dimensional case, leads to the appearance of an isostructural
phase transition line on the phase diagram.
A special feature of the multicomponentness is that the low-symmetry
phases increase in number. True, the highly truncated 17 4 and 17 6 models do
not permit description of all of the low-symmetry phases possible. As group-
theoretic analysis shows (§8), the solutions to the equations of state that arise
in these models correspond to the most symmetric phases of the possible dis-
symmetric phases. As allowance is made for invariants of higher degrees, an
156 CHAPTER 5
opportunity presents itself for describing dissymmetric phases of lower symme-

try.
A feature peculiar to problems with multicomponent OP's is that the
parameters of the potential increase dramatically in number when high-degree
invariants are taken into account. To obtain the stability regions of the result-
ing low-symmetry solutions, one has to impose certain relations between a large
number of phenomenological parameters. In this sense one may talk of more
probable and less probable dissymmetric phases. Indeed, the high-symmetry
solutions that occur in the 174 or 17 6 model depend on a smaller number of par am-
eters, and the constraints placed on these parameters by the reality and stabil-
ity requirements are not as rigid as those for the low-symmetry solutions that
arise in the 178 ,17 10 and higher-order models. Therefore such high-symmetry
phases in actual crystals should evidently occur much more frequently than
low-symmetry phases.
CUBIC INVARIANTS IN THE 17 4 MODEL
Now we construct a phase diagram for a thermodynamic potential with a two-

component order parameter and a cubic invariant. The treatment will be car-
ried out with the example of the potential
(17.31)
describing the structural phase transition in A-15 compounds (§13). We write

out the equations of state:
'h = 2r171 + v(317I - 317~) + 4u171 (17; + 17~) = 0,

(17.32)
1j2 = 2172 [r - 3v171 + 2u( 17I + 17~)] = 0,
and, on the basis of these, we find the types of solutions describing low-
symmetry phases different in symmetry. Recall that the search for the various
solution types can be made using the group-theoretic methods outlined in §8.
In addition to the zero solution, a total of five different solutions may be as-
sumed to exist for the potential (17.31), which is asymmetric with respect to
the OP components 171 and 172: (0,0) for phase 0, (±17, 0) for phase 1±, (0,17)
°
for phase 2, (17,17) for phase 3, (17, -17) for phase 4, and (171,172) for phase 5. We
check whether these types of solutions satisfy the equations of state. Phase
is a trivial solution of the equation of state. The solution (±17, 0) leads to the
quadratic equation for 17:
(17.33)
The next solution (0, TJ) substituted into equation (17.32) yields two equations:
-3VTJ2 = 0, 2rTJ + 4UTJ3 = 0,
which are compatible only at the point v = O.

The subsequent type of solution (TJ, TJ) transforms the equations of state to
r + 4U172 = 0, r - 3V17 + 4UTJ2 = 0, (17.34)
whence it follows that phase 3 (as well as phase 4) exists only on the line which
in parametric form is described by equations (17.34).
In the case of a general-type solution (TJ1, TJ2) we find that the equation
3v(3TJr - TJ~) = 0 holds, from which it follows that 3TJr = TJ~. The quantity is
determinable from the equation
(17.35)
It is easy to see by means of the substitution TJ1 = - h

that equation (17.35)
can be reduced to the equation (17.33) describing the (TJ,O) phase. The solu-
tions (TJ, 0), (--I3TJ,TJ) and (---I3TJ, TJ) lead, to within a change of variables, to one
equation of state for the parameter TJ. The low-symmetry phases correspond-
ing to these solutions have the same symmetry and differ from each other (as
shown in §8) only in the way they are inserted into the initial phase. Such a
situation is typical of multicomponent OP's and provides a basis for introduc-
ing the term 'solution type (TJ, 0)'. The angular brackets denote that several
equivalent solutions exist and the contents of the brackets coincide with one of
these solutions.
Thus the equations of state in the TJ4 model describe phase 1+ only, so in
the following we restrict ourselves to the solution (±TJ,O). We write down the
solution to the equation of state (17.33) for phase 1±:
TJ1 2 -
_ - -
3v ± [(3V)2 r ] 1/2
-8u - -2u . (17.36)
, 8u
From the condition for the square root to be positive, we find the region in
which the solution is real:
9v 2
r<-.
- 32u
(17.37)
The stability region of the solution (17.36) is found by the standard technique.
The region is determined by two inequalities:
VTJ ~ 0, 4r + 3VTJ ~ O. (17.38)

158 CHAPTER 5
The coefficient u will be assumed to be positive u > 0, for otherwise the

potential (17.31) will become negative at large values of TJ. The first of the
inequalities (17.38) means that when v < 0 the equations of state (17.33) have
positive solutions corresponding to phase 1+, while for v > 0 these equations
have negative solutions corresponding to phase 1-. The second of the inequal-
ities (17.38) coincides with the reality condition (17.37). The stability regions
of phases 1± on the (r, v) plane are sketched in Fig. 5.13. The initial phase 0
is stable in the upper half-plane, the stability region of the phases lies beneath
the parabola drawn by a dot-and-dash line. Since the stability regions of the
phases 0 and 1± overlap, the phase transition between them should be of first
order.
Fig. 5.13. Phase diagram for the TJ4 model with a cubic term in the
(r,v) plane.
The phase transition lines 0 +-!- 1± are found from the equality of the
thermodynamic potentials of the phases, (TJ) = o. This leads to the equation
r ± VTJ + UTJ2 = 0, (17.39)
which should be solved simultaneously with the equation of state (17.33). Thus
we obtain the relation between r and v:
v2
r=-, (17.40)
4u
which is shown in Fig. 5.13 by a solid line. The OP jump on this line is
(17.41)
We summarize some results of our investigation of phase transitions in the

TJ4 model. From the analysis performed, it follows that the presence of a cubic
invariant even in the 1J4 model leads to a first-order phase transition. A con-
sequence of truncating the series for the potential on fourth-degree invariants
was, as shown in the foregoing, the absence of a whole number of stable solu-
tions describing the low-symmetry phases. In the absence of cubic invariants
(potential (17.1)) the phase transitions from the initial phase to dissymmetric
ones are second-order transitions. To ascertain the character of the phase tran-
sition between two dissymmetric phases, higher-order terms should be added
to the potential.
CUBIC INVARIANTS IN THE 1J6 MODEL
Without enlarging on the intermediate calculations, we wish to see what hap-

pens as a result of adding the fifth- and sixth-degree invariants to the potential
(17.31). Consider the potential
 = r(rd + 1J~) + v(1J~ - 31Jr1J2) + u(1Jr + 1JD2+

+w(1Jr + 1JD(1J~ - 31Jr1J2) + Zl(1Jr + 1J~)3 + Z2(1J~ - 31Jr1J2)2.
We begin the analysis of the phase diagram with the phases 1±. The OP in
this phase satisfies the equation of state
(17.43)
We find the inequalities determining the stability region of this phase. The
matrix D, formed from the second-order derivatives of the potential with
respect to the variables 1Jl and 1J2, assumes diagonal form on substituting the
= =
solution 1Jl ±1J, 1J2 O. The stability conditions reduce to two inequalities:
±3v + 8u1J ± 15w1J2 + 24(Zl + Z2)1J 3 2: 0, (17.44)

±v ± W1J2 + 2Z21J 3 ~ O.
A major difficulty in analyzing the equations of state (17.43) and the stability
conditions (17.44) is that the solution of the quartic equation cannot be written
out in explicit form. Therefore, in keeping with the recommendations of §15,
we proceed in the following fashion.
We find the stability line of the phases 1±. To this end, we leave only
the equality sign in the inequalities (17.44). After a little manipulation the
equation of state and the first stability condition are then reducible to
r - 2U1J2 =F 5W1J3 - 9(Zl + Z2)1J 4 = 0, (17.45)

±3v + 8u1J ± 15w1J2 + 24(Zl + Z2)1J 3 = O.
160 CHAPTER 5
An explicit expression for the stability line can be found from the require-
ment that the resultant of the system (17.45) be equal to zero. Assuming the
parameter v to be small, it is however possible not to calculate the entire resul-
tant completely but to exploit perturbation theory [3]. As a result we obtain
the coupling between the parameters r, v, U, W, ..• as an expansion in powers
of v:
9v 2 5w 3
r= 32u + 2(8u)3(3v) . (17.46)
It is this coupling that determines the stability boundary of the phases 1± .

The second inequality (17.44) yields a system of equations
(17.47)
describing the second stability boundary of the phases 1±. Analogously, we

write these equations as an expansion in powers of v:
r = - ~ (_v)3 / 2
2uv ± __ (17.48)
W w 5/ 2
with ~ = 4UZ2 - w 2 . The lines (17.46) and (17.48) are shown in Fig. 5.14 by
a dot-and-dash line. From equation (17.48), it is seen that when ~ > 0 the
regions of existence of the phases 1+ and 1- do not overlap, and when ~ < 0
a region of coexistence of the phases 1+ and 1- occurs.
\~ .
r
l
-' ,,/
~/ II u
.<1/
--~~~-- "-",. ~~--------
f+
//
2 .
I
Fig. 5.14. Phase diagram for the T/6 model with a cubic term in the
(r, v) plane.
As has been shown in [3], the region of existence of phase 2 (solution type
(T/IT/2)) is bounded by the lines (17.48), so the phase transitions 1++-+ 2 and
1- +-+ 2 at ~ > 0 will be second-order phase transitions. For ~ < 0 phase 2
Fig. 5.15. Phase diagram for the rl model with a cubic term in the
space of the variables (r, v, A).
has no stability region. The phase transitions 0 +-+ 1+ and 0 +-+ 1-, just as in
the "14 model, will be of first order. The lines of first-order phase transitions
can also be found with the help of perturbation theory. In final form, the phase
diagram is presented in Fig. 5.15.
18. The Three-Component Order Parameter
THE PHASES AND THE STABILITY CONDITIONS
We conclude the analysis of phase diagrams with multicomponent order pa-

rameters by probing a phase transition that is described by the potential
(18.1)
This potential may be viewed as a direct generalization of the potential (17.1),

treated in the previous section, for the case of a three-component OP. The
universality of a potential of this form was clear from §14.
As in the previous example with the two-component OP, we begin the
analysis of the equations of state
<P7]} = 2"1dr + 2ul"1r + U2("1~ + 1J~)l = 0,
<P7]2 = 21J2[r + 2Ul1J~ + U2(1Jr + 1J~)l = 0, (18.2)
<P7]3 = 2"13[r + 2ul"1~ + U2("1r + 1J~)l = 0,
162 CHAPTER 5
by enumerating all the possible types of the different solutions. It is evident

that the following solutions are possible for the potential under consideration,
which differ in the relative value of the components 1Jl, 1J2, and 173:
o (000), 1 (1J 1J 1J), 2 (1J 0 0), 3 (1J 1J 0),

4 (1Jl 1J2 0), 5 (1Jl 1Jl 1J3), 6 (1Jl 1J2 1J3). (18.3)
To start with, we examine the lowest-symmetry phase, namely, phase 6.

The equations of state (18.2) for this phase (assuming all the 1J to be non-zero)
may be rewritten in the form
(2Ul - u2)(1Ji -1J~) = 0, (2Ul - u2)(l7i -1J~) = 0, (18.4)

(2Ul - U2)(1J~ -1J~) = 0,
whence it is seen that the general-type solution (1J11J2173) in the 1J4 model exists
only at the isolated point 2Ul = U2, while in the rest of the region of the
parameters .,., Ul, and U2 the system of equations (18.4) has the solution (1J 1J 1J),
which corresponds to phase 1. Similarly, it may be shown that in the 1J4 model
phase 5 coincides with phase 1, and phase 4 with phase 3.
We now explore the stability conditions for phases 1, 2, and 3. The stability
analysis reduces to determining those values of the parameters.,., Ul, and U2 for
which a given type of solution to the equations of state corresponds to a local
minimum of the potential (18.1). To this end, as was noted in §15, we should
require that all the principal minors of the matrix D constructed from the
second-order derivatives {)~/{)1J)..{)1J1' be positive definite. In the model being
considered (18.1) this matrix has the form
.,. + 6Ul1Jr + U2( 1J~ + 1J~) 2U21J11J2 2U21J11J3)

D = ( 2U21J11J2'" + 6Ull7~ + u2(1Jf + 1J~) 2U21J21J3
2U21J11J3 2U21J21J3'" + 6Ul1J~ + U2(1Jr + 1J5)
(18.5)
We start by considering phase 3. We substitute 1Jl = 172 = 1J, 1J3 = 0 into

equation (18.5) and use the equation of state (18.2) for phase 3:
(18.6)
The first stability condition follows from the requirement that the first principal
minor of the matrix (18.15) be positive definite. Allowing for equation (18.6),
this gives
(18.7)
The requirement that the second principal minor be positive definite gives us
the second stability condition for phase 3:
(18.8)
which splits into two systems of inequalities,
(18.9)
the second system of inequalities being incompatible in view of the fact that
Ul > O.
Finally, the third stability condition reduces to the requirement that the
determinant of the matrix D be positive definite. This leads to the inequality
(18.10)
Substituting the equation of state (18.6) into the inequality (18.10) yields
r
2Ul - U2
> 0. (18.11)
2Ul + U2 -
Taking into account the first and second stability conditions (18.7), (18.9), it
follows from this inequality that r ~ O. However, this requirement contradicts
the requirement that the solution to the equation of state (18.6) be real. Thus
phase 3 has no stability region in the T}4 model.
Consider now phase 1. On inserting the form of the solution T}l = T}2 =
T}3 = T}, corresponding to phase 1 in equations (18.2), we obtain the equation
of state for the parameter T}: r + 2( Ul + U2)T}2 = O. From this equation, we find
(18.12)
The first stability condition gives Ul > O. Allowing for Ul > 0, the second
condition leads to the inequalities
(18.13)
whereas the third stability condition yields
(18.14)
From the conditions for the solution (18.12) to be real, it follows that r < O.
Thus the stability region of phase 1 is determined by the inequalities
(18.15)
164 CHAPTER 5
Now we pass on to phase 2. The equation of state for phase 2 has the form
r + 2U1 'f/2 = 0 and the OP value for this phase is
2 r
'f/ = - - . (18.16)
2U1
The first stability condition gives U1 ;:::: O. The second condition reduces
to the inequality
(18.17)
which, allowing for the fact that the expression (18.16) for 'f/ is real, gives two
inequalities. In final form,
(18.18)
The third stability condition (positive definiteness of the determinant) is ful-

filled automatically provided the inequalities (18.18) are satisfied. Thus the
stability region of phase 2 is determined by the inequalities (18.18).
THE PHASE DIAGRAM IN THE 'f/4 MODEL
The stability regions of phases 1 and 2 are bounded by the inequalities (18.15)
and (18.18) respectively, as shown in Fig. 5.16. The dissymmetric phases 1
and 2 border on each other on the U1 = U2/2 plane. Just as in the case of a
two-component OP, it is impossible in the 'f/4 model to solve the problem of the
phase transition between these phases. Indeed, the equality of the potentials
<'P('f/ 0 0) = <'P('f/ 'f/ 'f/) leads to the expression
r 2 ( 2u 1 - U2) _ 0
(18.19)
U1(U1 + U2) - ,
which does not give the coupling between all the three coefficients r, U1 and
U2. From the condition for the potentials of phases 1 and 2 to be equal to zero,
we find that the phase transitions 0 ~ 1 and 0 ~ 2 are second-order phase

transitions and that the lines of these transitions lie in the r = 0 plane. A
complete phase diagram in the 'f/4 model is presented in Fig. 5.16.
Allowance for the invariants of degree six, which have the form
( 'f/12 + 'f/22 + 'f/32)3 , 'f/12'f/22'f/32, [4(

'f/1 'f/22 + 'f/32) + 'f/24( 'f/12 + 'f/32) + 'f/34( 'f/12 + 'f/22)] ,
leads to the occurrence of first-order phase transition lines 0 ~ 1 and 0 ~ 2
in the phase diagram, as in the case of a two-component OP. At certain values
Fig. 5.16. Stability regions of phases 1 and 2 for the potential (18.1)
with a three-component order parameter.
of the coefficients of the thermodynamic potential a phase 3 wedges itself in

between the phases 1 and 2 (in the 'f/4 model the corresponding solution exists
in the Ul = u2/2 plane, but it is unstable). A detailed analysis of a potential
with a three-component OP, taking into account invariants of degree six, is
contained in [9]. That paper quotes the stability regions of phases 1, 2, and 3,
and also the OP values for each of the phases.
19. The Role of the IRBI in the Construction of Phase Diagrams
Exploiting the concept of the IRBI enables one to view the phase diagram
construction methods in a different light. We wish to enumerate the chief
advantages that the IRBI technique can provide in this problem. First, finding
the IRBI permits the thermodynamic potential to be immediately expanded
up to any power desired. Second, a knowledge of the IRBI enables one to single
out those terms of a given degree in the potential ~ that account for qualitative
changes in the phase diagram. Third, the utilization of the IRBI may come
to play an essential role in probing low-symmetry dissymmetric phases. As
shown in the foregoing sections, such phases occur in phase diagrams only
when invariants of sufficiently high degrees are allowed for in the potential.
The technical difficulties that arise here naturally lead us to the desire to learn
to what lowest degree we can confine ourselves without losing the phase of
interest.
166 CHAPTER 5
THE TWO-COMPONENT ORDER PARAMETER
As an example of IRBI applications, we consider the potential explored in §17.

This potential, as was shown in §13, corresponds to the group I = C 3v , and
the IRBI for this group is composed of two invariants:
(19.1)
The full polynomial expansion for the potential may be represented as
(19.2)
We write out the equations of state, regarding as a composite function of 771
and 772, in terms of the invariants 11 and 12 :
{) / {)771 = 2~ 771 + 3~ (77f - 77~) = 0,

(19.3)
{)/{)772 = 2772[~ - 3~77d = 0,
where the derivatives with respect to the invariants of the series for are
{) 2
= {)I1 = r + 2U1h + wI2 + 3z 1 I 1 ,
I _
1
(19.4)
I {)
2 == {)h = v + wl1 + 2z 2 12 .
(The use of the minimization of the potential with respect to invariants was
first proposed in [10]). Without placing in advance any constraints on 'T}1 and
772, it is easy to see from the equations of state (19.3) that in the case of ~ -:f. 0
and ~ -:f. 0 the formal solution has the form
(19.5)
which, just as in the 'T}4 model (§17), corresponds to a solution of the type
(±77 0) (phase 1±).
To obtain equations for finding a general-type solution, we should require
~ = 0, ~ = O. (19.6)
As follows from the explicit form of the expressions (19.4) for ~ and ~, the
system of equations (19.6) may yield solutions for 'T}1 and 'T}2 provided only
that at least the fifth-degree invariants are allowed for in the potential (19.2).
However, truncating the potential at degree five results in the possibility that
at positive values of the parameter wand at negative values of the expression

(1]f - 31]11]~) (or conversely) the potential cI> may become negative at large
values of 1]1 and 1]2. To describe a (1]11]2) type phase, it is therefore necessary
to take into account also the invariants of degree six, that is, to analyze the
potential (19.2). In §17 it was just shown by a straightforward calculation that
the low-symmetry phase exists for this potential only in the 1]6 model.
THE THREE-COMPONENT ORDER PARAMETER
As another example, we consider the IRBI for the group 1 = Oh. This basis
consists of three invariants (§14):
(19.7)
We construct the potential as an expansion in the IRBI:
(19.8)
(With allowance for fourth-degree invariants only, this potential was treated in
detail in §18.) We write out the equations of state
OcI>/01]l = 21]dcI>~ + 21]rcI>~ + 1]~1]~cI>~l = 0,

OcI>/01]2 = 21]2[cI>~ + 21]~cI>~ + 1]I1]~cI>~l = 0, (19.9)
OcI>/01]3 = 21]3[cI>~ + 21]~cI>~ + 1]I1]~cI>~l = 0
in terms of the derivatives of cI> with respect to the invariants h, 12, and h:
cI>~ == ocI>/oh = r + 2U1h + 3W11[ + w212 + ... ,
cI>~ == ocI>/oI2 = U2 + w212 + ... , (19.10)
cI>~ == ocI>/oI3 = W3 + ....
All the solution types possible for the potential (19.8) are listed in §18. Corre-
sponding to the lowest-symmetry phase 6 (solution type (1]11]21]3)) is the system
of equations
cI>~ = 0, cI>~ = 0, cI>~ = O. (19.11)
Note that in the notation of the equations of state (19.9) a general-type solu tion
always reduces to the requirement that cI>: = O. It follows immediately from
the expressions (19.10) for cI>i that the lowest degree that should be taken
into account in the thermodynamic potential in order to obtain a general-type
sol u tion (1]11]21]3) is the eighth.
168 CHAPTER 5
The equations of state for phase 4 (solution type (171 172 0)) reduce to
~ = 0 and ~ = O. Again, it is immediately seen from the expressions (19.10)
that allowance for invariants of degree four alone, as made in §18, gives no
unambiguous solution for the parameters 171 and 172. To obtain the relevant
solution, it is necessary, at least, to allow for invariants of degree six.
Let it be emphasized that even on determining the lowest degree at which
the series for should be truncated to obtain the solutions of interest, we still
have no guarantee that a given phase will have no finite stability region, as was
the case with phase 3 (17 17 0) in the 174 model.
20. Coupling Order Parameters
THE INTERPLAY OF TWO ONE-COMPONENT ORDER PARAMETERS
Examples are known of an observed phase transition being incapable of de-

scription by a single order parameter that transforms according to one IR. Such
examples are particularly numerous in magnetic crystals, when the magnetic
structure is described by two or more IR's. Structural phase transitions whose
description requires several OP's have been found to occur in KMnF 3 [11],
boracites, and other materials. The thermodynamic potential in these com-
pounds should be constructed from powers of coupled OP's including mixed
terms.
A similar problem arises when we wish to analyze the behavior at the
phase transition point of physical quantities that are not OP's. Examples of
such problems include an analysis of the magnetostriction at a magnetic phase
transition, an analysis of strain tensors and elastic moduli at structural phase
transitions, an analysis of crystal atom displacements at proper ferroelectric
transitions as well as an analysis of the polarization at improper ones, etc.
To bring out the major features peculiar to the problem with two OP's, we
consider the simplest model. The potential corresponding to this model is of
the form [12]:
(20.1 )
The equations of state
(20.2)
allow three types of solution:

1. 7]
2 Tl
= --,
2Ul
e= 0;
2. 7]- 0
-,
e - --'
2
-
T2
2U2' (20.3)
2 T2 W - 2U2Tl c2 Tl W - 2U1T2
3. 7] = d , .. = d '
with d = 4Ul U2 - w 2 . From the expressions (20.3) we find the regions in which
the solutions (20.3) for phases 1 to 3 are real:
1. < 0, Ul > 0;
Tl
2. T2 < 0, U2 > 0;
(20.4)
3. T2W - 2U2Tl > 0, T1W - 2U1T2 > 0 (d > 0);
T2W - 2U2Tl < 0, T1W - 2U1T2 < 0 (d < 0).
The stability regions of these phases are determined by the inequalities
(20.5)
Simultaneously with the conditions of existence (20.4), they have the form
1. rl::; 0, 2Ul T2 - WTl 2: 0;

2. T2::; 0, 2U2Tl - wr2 2: 0; (20.6)
3. d > 0, T2W - 2U2Tl 2: 0, Tl W - 2Ul T2 2: O.
Phase diagrams in the (rl,T2) plane are presented in Fig. 5.17. From the in-
equalities (20.6), phase 3 is seen to be stable in the interval (d > 0) -2v'U1U2 <
W < 2v'Ul U2. In this range of values of the interaction coefficient W of the pa-
rameters 7] and e, a phase diagram is realized which has a tetracritical point
(Fig. 5.17a and b). In the case of d < 0, that is, at large values of the coupling,
a phase diagram with a bicritical point is realized (Fig. 5.17 c) [13].
A number of features should be noted for the phase diagrams obtained.
Inspection of Fig. 5.17 shows that in terms of the model considered, which
contains only invariants of degree four, phase transitions 1 +-+ 3 or 2 +-+ 3 are
second-order transitions. On the other hand, experimental data are available
that indicate that such transitions sometimes proceed as first-order transitions.
Note also that a second-order phase transition 0 +-+ 3 is possible only at a point
in the plane of the variables (TX). In a variety of materials, however, the
transition line 0 +-+ 3 is observed. This applies, for example, to the magnetic
phase transition in the oxides MnO, FeO, etc. [14].
170 CHAPTER 5
2 II 1; 0
-~~. . L=-~=~2
/'1 f
./ /
i
(a) (b) (c)
Fig. 5.17. Phase diagram in the case of two order parameters: (a)
.6. > 0, 2(U1U2)1/2 > w > 0; (b) .6. > 0, -2(U1U2)1/2 < w < 0; (c)
w > 2( Ul U2)1/2. The dot-and-dash line represents the phase stability
boundary; the dashed line represents second-order transitions; the
solid line represents first-order transitions.
To describe the experimental facts noted above, it suffices to add to the

potential (20.1) the invariants of degree six:
(20.7)
A complete analysis of the potential (20.7) according to the technique outlined

in §15 (see also [3]) shows that, just as in the case of one OP, allowance for
invariants of degree six permits description of first-order phase transitions from
the initial phase 0 to phases 1, 2, and 3 (Fig. 5.18). Adding the terms Vl1]6 and
V2~6 leads also to the phase 3 becoming stable at large values of the interaction
parameter w > 2( Ul U2)1/2 (Fig. 5.18). Certainly, the first-order phase transi-
tions which are observed experimentally instead of the second-order transitions
predicted by the Landau theory may be explained in particular cases by other
causes as well, for example by the coupling of the OP with another subsystem
of the crystal. However, the fundamental possibility of accounting for these
phenomena by higher-degree invariants should also be borne in mind.
PHASE TRANSITIONS IN MnAs
It was shown in the foregoing that at certain ratios for the thermodynamic
potential coefficients a phase diagram with a bicritical point is realized (Fig.
5.17c). This type of phase diagram corresponds to the situation where the
sequence of transitions occurring in the crystal when the external parameters
are varied is first 0 +-+ 2 and then 2 +-+ 1. Some sort of a supplanting of one
2 r,
...........
J ---
\ 1
'2
---:; f
I
(a) (b)
e
Fig. 5.18. Phase diagrams in the "76 and 6 models for: (a) Ul < 0,
U2 < 0, -2(U1U2)1/2 < w < 0; (b) Ul > 0, U2 > 0, W> 2(U1U2)1/2.
parameter by another should be observed in experiment. It is this situation

that occurs in MnAs.
At Tt ~ 400I< a structural phase transition takes place in MnAs [15] at
which the NiAs type structure (space group D~h) is succeeded by a structure
such as MnP (D~~). Then, at Tc ~ 310I<, a magnetic ordering occurs which is
accompanied by formation of a collinear ferromagnetic structure with spins in
the basal plane, the crystal structure reverting to the initial structure. From an
analysis of the superstructural reflection indices, it is seen that the structural
transition is described by the wave-vector ~l = ~bl (star {~12}), and the
magnetic transition by the wave-vector ~ = 0.
Knowing the initial-phase symmetry group D~h' the dissymmetric-phase
symmetry group D~~ and the wave-vector star over which the transition goes,
it is easy to see by the standard group-theoretic method that the structural
transition in MnAs is described by the three-dimensional IR T4 of the star
{~12}. The magnetic structure that occurs in MnAs is described by the two-
dimensional IR Tg of the Brillouin zone point r.
To describe the sequence of transitions observed, we construct a poten-
tial that corresponds to the system of coupling OP's "7 (structural) and e
(magnetic) [15]:
 = rl("7i + "7~ + "7D + r2(ei + e~) + Ul("7t + "7i + 7]j)+

+u2(ei + e~)2 + u3("7i"7~ + 7]i"7~ + 7]~7]~)+
+w(ei + e~)(7]i + "7~ + 7]~). (20.8)
172 CHAPTER 5
We write out the equations of state o / orJ).. = 0 and o / 06 = 0:
+ 2U1rJ? + U3(rJ~ + rJ5) + w(e? + e~)] = 0,

2rJdrl
(20,9)
2e1h + 2U2(e? + en + w(rJ? + rJ~ + rJ5)] = 0,
The other equations are obtained from the equations of state (20,9) by cyclic
permutation of the parameters rJ).. and 6, The solutions to the equations of
state describe phases 0 through 7, which have different symmetry:
0: rJ1 = rJ2 = rJ3 = 0, e1 = 6 = 0;

1 ', ,,2
'11 -- r1 , "
-- ,,2 -- , ,
,,3 -- 0, ..c1 -- ..c2 -- 0',
2U1
2 2 r1
2: rJ1 = rJ2 = -
2U1 + U3
, 6 =6 = 0;
3 ,' c - c - 0'
,,2 -
"I -
,,2
,,2 =
,,2 _
,,3 - - 2( U1 + U3)'
r1
.. 1 - .. 2 - ,
4 ', "
"I -
- ,,
,,2 -
- " c 2 + "2
,,3 -- 0 '''1 c2 -_ r2,
-- ,
2U2
5: 2 - 2U 2r 1 + wr2 0 c2 c2 r1 w - 2U1r2
rJ1 = .6. ' rJ2 = rJ3 = '''1 +"2 = .6. ;
6: 2 2 wr2 - 2U2r1 0 c2 c2 2wr1 - (2U1 + U2)r2
rJ1 = rJ2 = .6. ' rJ3 = '''1 + "2 = .6. 1 ;
7 ', 2 2 2 r2 w - 2U2r1 c2 c2 3W1'l - 2r2(Ul + U3)

rJ1 = rJ2 = rJ3 = .6. 2 , "1 +"2 = .6. 2 ,
(20,10)
where .6. = 4U1 U2 - w 2, .6. 1
= 2(2u1 + U3)U2 - 2w 2, .6. 2
= 4( U1 + U3)U2 - 3w 2,
Three phases are realized in the example under consideration, These are
0, 1, and 4, Phase 4 is a magnetically ordered phase with restored crystalline
structure, The first-order transition line 1 +-+ 4 is found from the energy equal-
ity condition and is described by the equation
(20,11)
On this line the structural parameter rJ2 = -r~(1t - Tc)/2u1 is succeeded by

the magnetic one, The jump of the magnetic OP is
(20,12)
The ratio of the structural and magnetic OP's on this line depends only on the
ratio UI/U2, which can be determined experimentally,
\Ve conclude by making one more statement concerning the example con-
sidered, From experimental data on the magnetic transition in MnAs, it follows
that the crystalline symmetry of the magnetically ordered state coincides with
the symmetry of the initial phase. The possibility itself of there existing a
magnetically ordered phase with the same crystalline symmetry as that in a
non-magnetic phase is known to be present only in the case of a magnetic
transition according to a one-dimensional representation (in keeping with the
Niggli-Indenboom theorem [16]). At the same time the analysis performed
above shows that the relevant representation at a magnetic phase transition
in MnAs is two-dimensional rather than one-dimensional (the collinear ferro-
magnetism in the basal plane in a uniaxial crystal is always associated with the
two-dimensional representation). True, the potential as a function of two OP
components up to fourth-order terms inclusive depends only on the sum of the
a
squares of these components +e~, that is, is quasi-dependent on the quantity
e alone. This corresponds to the situation where the magnetic anisotropy in
the basal plane in a hexagonal crystal is described only by invariants starting
with degree six. Thus the one-component ness of the magnetic OP is justified
only to within fourth-order invariants. On the other hand, although the fact
of the crystal symmetry being restored at the magnetic transition is held to be
experimentally established, it is clear that this fact is true only to within some
experimental accuracy, namely up to anisotropic sixth-order invariants again.
No exact symmetry restoration may occur here, for we deal with the collinear
ferromagnetism in the basal plane, and therefore, on account of the lattice ad-
justing itself inevitably to the magnetic order that arises, the symmetry of the
crystal cannot become higher than the orthorhombic symmetry.
PHASE TRANSITIONS IN KMnF 3
Now we consider an example in which a phase diagram with a tetracritical point

(Fig. 5.17) is realized. The familiar perovskite crystal KMnF 3 is remarkable
specifically for exhibiting a series of successive structural and magnetic phase
transitions as the temperature is lowered. First, at temperature Tel = 188.6K
a tetragonal distortion arises which precedes the emergence of a soft mode, and
then, at Tc2 = 91.5K, an additional tetragonal distortion occurs. Shortly after
the second structural transition the next successive type undergoes magnetic
ordering. At temperature 111 = 88.3K a collinear antiferromagnetic structure
arises in which the magnetic moments are oriented along the initial-phase cube
edge parallel to the tetrad axis of the distorted crystal, and at a temperature
equal to 81.5K an orientational magnetic transition occurs in which the mag-
netic moments lie in the basal plane. Also, the occurrence of a transverse weak
174 CHAPTER 5
ferromagnetism at a temperature below T.l is noted [17] .
• - K
II- - Mn
O-F
Fig. 5.19. Motion of fluorine atoms in the unit cell of KMnF 3 . • , K;

x, Mn; 0, F.
The crystal structure of KmMnF 3 is specified by the atomic positions K( 1),

Mn(l), and F(3) of the group OJ; (Fig. 5.19). It has been found experimen-
tally that for the most part the atoms of fluorine, which form octahedra, are
displaced at both structural transitions, these displacements being described
in the first approximation by the rotation of the octahedra through some angle
about one edge of the cubic unit cell. In the adjacent cells the octahedra rotate
(in the first transition) in opposite directions (at Tc2 < T < Tcd. In the second
transition the octahedra aligned with the axis of rotation rotate in the same
direction, while the adjacent octahedra oriented perpendicular to the axis of
rotation rotate in different directions. Thus when Tc2 < T < Tel the unit cell
doubles along all the three directions, and when T < Tc2 a new distortion is
added to this doubling. The new distortion is characterized by doubling of the
initial cell in two directions perpendicular to the axis of rotation.
It is easy to show that the distortions described above are characterized
by one-arm wave-vector stars at Tel and by three-arm wave-vector stars at Tc2
[17]:
only one star arm, for example ~1, participating in the second transition. The
magnetic structures arising at the points 111 and T.l are characterized also by
the star {~13}.
In order to construct the potential describing the phase transitions in
KMnF 3 , it is necessary to determine by which IR each of the transitions is
described. By calculating the magnetic and structural modes according to the

formulas given in §3 and exploiting the above description of the phase tran-
sitions, one can readily establish [11] that the soft mode, which leads to a
structural transition at the point Tel, has the symmetry 78 of the star {,d3}.
In addition to this, a similar motion of the octahedra arises at the point T c2 ;
this motion is described by the basis function of the one-dimensional IR 75 of
group Ok star {,d1} on arm ~1. The magnetic structure arising at the points
T 1. and 711 is described by the modes of the three-dimensional representation 78
of the star {~13}. We start by considering the interplay of the OP's of the first
structural phase transition with the magnetic transition OP's 6,. It is easy to
write down the corresponding thermodynamic potential [17,18]:
 = ~1''1 (1]r + 1]~ + 1]~) + tUI (1]{ + 1]i + 17i) + ~U2( 1]r1]~ + 1]r1]~ + 1]~1]~)+
+~1'e(~r + ~i + ~~) + t Vl(a + ~i + ~i) + ~V2(~~~~ + a~~ + ~~~~)+
+~wl(1]i~r + 1]~~~ + 1]~~~) + ~w2[1]i(~~ + ~D + 1]~(~i + ~~) + 1]~(~i + ~~)]+
+W3(1]1172~16 + 1721]366 + 1]31]166), (20.13)
where 1''1 = 1'~(T - T~) and 1'e = 1'€(T - T~,) with T~ and T,~, being the "bare"
temperatures of the structural and the magnetic phase transition in the absence
of a coupling between them.
Each phase is characterized by a six-component vector (1]1, 1]2,1]3,6,6,6).
We investigate the conditions for the succession of the three phases (1 to 3)
observed experimentally:
1) (1] 0 0, 000) 711 < T < Tel;

2) (1]11 0 0, ~II 00), TJ. < T < 'Ill; (20.14)
3) (1]1. 00, 0 0 ~J.), T < TJ..
By minimizing the potential (20.13), we find the expressions for the OP's,
transition temperature, and energy of each of these three phases, as well as the
stability conditions for them:
Phase 1
1] 2 -_ _ 1''1 , (20.15)
Ul
a 1 1''1
Tel = Tc ' 1 = -4'-, (20.16)
UI
Ul > 0, U2 - UI > 0; (20.17)
Phase 2
2 -1''lVI + 1'e W I ('2 _ _ 1'e U I + 1''lWI (20.18)
1]11 = Ul VI - wi '''II - UI VI - Wf '
176 CHAPTER 5
(20.19)
(20.20)
UI > 0, UI VI - wi > 0, (U2 - Ut)17~ + (W2 - Wt)~~ > 0, (20.21)

[(U2 - UI)17~ + (W2 - Wt)~~][(V2 - vt)~~ + (W2 - WI)17~]- W~17II~11 > OJ
Phase 3
(20.22)
Tl. = T! - Dl.(T~ - T!),

Dl. = r~(wl - tW2)[(1- t)uIr{ - (WI - tW2)r~]-1, (20.23)
t = (UIVI - wi)I/2(UIVI - wD- I/ 2,
<1>3 - _ rl _ 1 (r€ - r7)wdut)2

- 4UI 4 VI - WVUI ' (20.24)
UI > 0, U2 - UI > 0, V2 - VI > 0, UI VI - w~ > 0,
(20.25)
[( U2 - Ut)171. + (WI - W2)~1.][( V2 - vt)~1. + (WI - W2)17rJ - w~17H1. > O.
The conditions for the experimentally observed sequence of phase transi-

tion temperatures Tl. < 111 < Tel (at T;; < T~) reduce to
(20.26)
The phase transition at the point Tel is, as can be seen from the expression
(20.15), of second order, like the 1 f-t 2 transition at the point 111' The phase
transition 2 f-t 3 at the point Tl. turns out to be a first-order transition. The
transition temperature (20.23) is found from the equality of the thermodynamic
potentials <1>2 and <1>3. The OP jumps at T = Tl. should be related by the
equations [17,18]
17IT _ 1- (1 + DJ:I)(wIr~)/(vIr{) ~~
(20.27)
171. 1-(1+D.LI)(w2r~)/(vIre)· ~1'
C4 2
"'II _ UI VI - W2 _ -2 1 (20.28)
e1 - UI VI - Wi - t <.
This applies to the point T = Tl.. At the point T = 111 the magnetic OP
that arises is of second order, the structure parameter being continuous. The
temperature behavior of the OP in KMnF 3 is sketched in Fig. 5.20. Dis-
continuities of the structural OP at the point Tl. were observed in a neutron
diffraction study on a KMnF 3 single crystal, where a magnetic peak intensity
hysteresis was also detected indicating a first-order phase transition at the same
point [17]. This theory of the coupling of two OP's enables one to understand
the regularities observed in the structural and magnetic phase transition in
KMnF 3 .
Fig. 5.20. Temperature dependence of the structural TJ and magnetic

e order parameters in KMnF 3 (shown schematically).
In the foregoing analysis we have disregarded the second structural tran-

sition occurring at the point Tc2 and investigated the interaction of the first
structural transition with the magnetic transition. Now we wish to illustrate
the coupling of both structural transitions; but in order not to encumber our
analysis, we will neglect the magnetic phase transitions.
As has already been stated, structural distortions arise at the point Tel
in KMnF 3 which are due to the displacement of F atoms and are specified
by the star {ld3} (Brillouin zone point R). At a lower temperature, at T c2 ,
the crystal suffers a new distortion which arises from extra displacements of F
atoms and is described by the star {ld1} (Brillouin zone point M). We need to
write a thermodynamic potential that depends on two OP's. It is convenient
to represent these as R).. (A = 1,2,3) and M).. (A = 1,2,3) respectively. As
can be readily seen, mixed terms of the form R~M'1. may be used to set up
178 CHAPTER 5
invariants since the law of conservation of momentum holds (to within the
parent-crystal reciprocal-lattice vector) for such terms. Displacements of F
may bring about displacements of other light atoms, primarily those of K.
Such light-atom displacements were detected experimentally at T < Tc2 [19].
Let some OP X>. correspond to this type of displacement. The occurrence of
these displacements in the phase where the OP's R>. and M>. were condensed
calls for invariants such as RM X. It follows from the law of conservation of
momentum that the parameter X should be specified by the star {,dOl:
(20.29)
(Brillouin zone point X).

Thus the problem arises of describing the coupling of the three OP's,
R>., M>., and X>. (the observed K ion displacement along the cube axes is
specified by the one-dimensional IR 74 of the group G" [20], so X>. refers to the
three-dimensional IR and A = 1,2,3). The situation that has been described
corresponds to the thermodynamic potential [20]
 =r L R~ + Ul L R1 + U2 L R~R~ + r' L M~+

>. >. >'<1-' >.
+u~ L M;, + u~ L M~ M; + J( L X~ +V L R>.M>.X>. + ... , (20.30)

>. >'<1-' >. >.
where r '" (T-Tcd, r' '" (T-Tc2)' and all the other parameters depend weakly
on temperature. Minimization of with respect to X>. yields the equation
(20.31 )
which shows that the displacement of K atoms should accompany the displace-
ment of F atoms in the R + M phase at T < T c2 . Since the coefficient J( is
temperature independent, the parameter X>. is not an OP in the strict sense
of the word; the X>. may be called a concomitant OP. The crystal distortion
that is associated with it does not change the phase symmetry at T < T c2 . The
space groups of the various dissymmetric phases are as follows:
(20.32)
ORIENTATION TRANSITIONS
The term 'orientation transitions' is employed to describe transitions in molecu-

lar crystals and magnetic phase transitions. In the first case the phase transition
consists of either a spontaneous alignment of molecules relative to each other

at the phase transition point or a change in their relative orientation. In the
second case the term 'orientation transitions' (sometimes called 'reorientation
transitions') is associated with a change in magnetic moment direction.
The orientational magnetic transitions may be broken up into two classes:
spontaneous transitions and induced transitions. In the case of spontaneous
orientation transitions a change in the direction of magnetic moments is due to a
change in temperature. Induced transitions are orientational phase transitions
in a magnetic field.
The spontaneous orientation transitions, in turn, may be divided into those
described by one irreducible representation of the paramagnetic-phase symme-
try group and those described by two coupling OP's. In both cases the phase
transition results from a change of the magnitude and signs of the magnetic
anisotropy constants [21,22].
Orientational phase transitions described by one IR occur in cubic mag-
netics. The simplest thermodynamic potential has the form
 = 1'1(17r + 17~ + 17~) + U1(17r + 17~ + 17~)2 + U2(17r17~ + 17i17~ + 17~17~)+
+V1(17i + 17~ + 17~)3 + V217i17~171+
+V3[17r17~(17r + 17~) + 17i17~(17i + 171) + 17~171(17~ + 171)]' (20.33)
where 171, 172, 173 may be viewed as magnetization vector components. Po-
tentials of this kind were explored in detail in the preceding sections. In the
construction of a phase diagram, no restrictions are imposed in the general case
on the value of the vector 11 = (171,172,173) or its angular position. A distinctive
feature of a thermodynamic description of orientational phase transitions is
that the magnitude of the magnetization vector is normally assumed to be in-
dependent of temperature. Only the angular dependence of the magnetization
vector is investigated. It is therefore convenient to choose direction cosines Cti
as the variables: 17i = 17Cti and to write the potential (20.33) in the form
(20.34)
with (17) the isotropic part of the potential; J{l and J{2 anisotropy constants,
which are some combinations of the starting parameters Ui and Vi.
The potential (20.34) describes three phases: phase I with the magneti-
zation vector along [100], phase II with the magnetization vector along [110],
and phase III with the magnetization vector along [111]. The phase diagram
180 CHAPTER 5
portrayed in Fig. 5.21 indicates at what values of the anisotropy constants ](1
and ](2 each of the aforecited phases occurs. Thus the model (20.34) under
consideration describes orientational first-order transitions (If-tIII and IIf-tIII)
and orientational second-order transitions (If-tII) between phases with fixed
magnetic moment direction.
~K.~I(=DI
"", j _1. I
" !! I I
" I
I
________~~I~-------- J'l
Fig. 5.21. Phase diagram of orientational transitions in cubic mag-

netics.
Adding invariants of higher degree will lead to the appearance of new

phases with an arbitrary magnetization vector direction. Thus addition of the
invariant
(20.35)
to the potential (20.34) will lead to the appearance of two angular phases in
the phase diagram: phase IV with the magnetization vector along the [u v 0]
direction and phase V with the magnetization vector in the general direction.
The stability regions of phases IV and V are determined by the inequalities
[22]:
Phase IV:
(20.36)
Phase V:
Phases I-V occur in HoxEr1_xFe2) the phase diagram of which is presented in

Fig. 5.22. Phases IV and V have been found to occur also in Laves-type phases
RF 2. A detailed review of orientational phase transitions in cubic magnetics is

available in a monograph [22].
Consider now orientational phase transitions described by two coupling
OP's. Typical representatives of such transitions are those in rare-earth or tho-
ferrites RF0 3 (R stands for rare-earth elements). The potential may be chosen
in the form (20.1)
(20.37)
e
where TJ and may be regarded as two magnetization vector projections. Since
the symmetry group of RF0 3 is a rhombic one, each magnetization vector
projection transforms by its individual one-dimensional IR, and this is what
determines the choice of the potential in the form of equation (20.37).
300
200
100
o 02 04 06 08
Fig. 5.22. Phase diagram of HoxRrl-xFe2, obtained from measure-

ments of Mossbauer spectra and elastic moduli.
To describe orientational phase transitions it is convenient, as in the pre-

vious case, to pass on to new variables, TJ = p sin I/J and TJ = P cos I/J, and
to restrict attention to the magnetization vector orientation. The potential
(20.37) in terms of the variables p and I/J transforms to
(20.38)
and the equations of state have three solutions:
Phase I: B = 0, 7T; /{l ~ 0;

7T 37T
Phase II: B = 2'"2; /{l + 2/{2 ~ 0; (20.39)
. 2 /{l
Phase III: sm B = - 2/{2 ; /{l ~ 0, /{l + 2/{2 ~ O.
182 CHAPTER 5
For J{2 > 0 all the three phases have stability regions. In the case of J{2 < 0
phase III is unstable.
The results cited above coincide with the more general results (20.35) and
(20.36). Phases I and II are virtually (77 0) and (0 e) type phases. Phase III
is a phase of type (77 e). Just as in the preceding case, the directions of the
magnetization vector in phases I and II coincide with one of the crystallographic
directions. Phase III is said to be angular; it corresponds to an arbitrary
magnetization vector direction. The temperature dependence of the anisotropy
constants J{i leads to continuous rotation of the magnetization vector in phase
III as the temperature is varied. Experimental data on rare-earth orthoferrites
are reviewed in [22].
We consider the main properties of induced orientation transitions. As
already stated, induced transitions are orientation transitions induced by an
external field H. The influence of an external field on a magnetic structure
depends on the type of structure considered.
Consider orientation transitions in antiferromagnetics. The major features
peculiar to the behavior of antiferromagnetic structures in an external field
may be illustrated by the example of a two-sub lattice anti-ferromagnet. This
is usually described by the magnetization vector M = MI + M2 and antiferro-
magnetism vector L = MI - M 2, where MI and M2 are the magnetization
vectors of the sublattices 1 and 2. As in the previous example, we assume the
effect of an external field to reduce only to rotation of the vectors Ml and M2
and to a change of the angle between them, the length of the vectors remaining
constant: MI = M2 = M. We assume also that the vectors M I , M 2 , and H
lie in the same plane (Fig. 5.23) and the anisotropy axis coincides with the
z axis. It is convenient to write the thermodynamic potential in terms of the
variables MI and M 2:
(20.40)
where A is the exchange interaction parameter, a and b the anisotropy para-

meters. Suppose that lal, Ibl ~ A.
Note that in choosing the potential (20.40), we have departed from the
usual potential construction procedure outlined in §15, where mixing coeffi-
cients of definite modes of the relevant IR are chosen as the OP's. This digres-
sion is dictated by the specific nature of the problem solved. Namely, we do
not explore conditions under which a given magnetic structure is liable to arise
from the paramagnetic phase; nor do we investigate the effect of an external
Fig. 5.23. Relative position of the vectors L, M, M2 and H in the

(xz) plane.
field on the occurrence of that structure. Instead, we are concerned with the
relative position of magnetic moments in a magnetic structure of a given type
as a function of the orientation of the applied field H. In the general case a
potential such as (20.40) can be obtained in the usual way. That is, using the
IRBI method (see §12), a potential symmetric under the paramagnetic-phase
symmetry group is constructed for a specific crystal. Then we substitute into
this potential the OP corresponding to the magnetic structure type chosen,
impose the conditions for the magnetic moments to be constant and obtain, as
a result, a potential of the form (20.40).
To start with, we consider the cases H " z and H ..L z (1jJ = 0, 7r /2). Since
the position of the vectors L, M 1 , and M2 is unambiguously prescribed by the
angles () and e/; (Fig. 5.23), we seek the equilibrium position of the vectors Ml
and M2 in the equations
8'P 8'P
8() = 0, 8e/; = O. (20.41)
In the case of H II z (w = 0) equations (20.41) allow three solutions:

I. ()=O, e/;=O (Lllz);
I () 7r • A. H
I. =2,SIll'l'=(2A_a_b)M (L..Lz); (20.42)
7r 7r
III. 0 < () < 2' 0 < e/; < 2'
The stability conditions
(20.43)
184 CHAPTER 5
determine two critical fields Hl and H 2:
(20.44)
where Ho = M ((2A - b) (a - b) r/2. For H :::; H2 phase I is realized, and when

H > Hl phase II occurs. The realization of phase III depends on the ratio and
signs of the constants a and b. In the case of a> 0, H2 > Hl and phase III is
unstable. In the interval .D..H = H2 - Hl = tHo the stability regions of phases
I and II overlap and the phase transition I+--tII is a first-order transition. In
the opposite case a < 0, H2 < Hl and phase III occurs over the field range
H2 :::; H :::; H l . At H2 :::; H :::; Hl the vector L rotates from the z axis to
the x axis. When H > Hl the vector L continues to remain parallel to the
x axis, but decreases in magnitude. On reaching H = Hl~ = M(2A - a - b),
the vectors Ml and M2 flop, the vector L vanishes, and a so-called 'spin-flop'
transition comes about.
Only one state, specified by L II z (8 = 0, ¢ ::ft 0) occurs in the case of
H J.. z ('1jJ = ~). As the field H is increased the vector L decreases in magnitude
due to envelopment of the vectors Ml and M2 (angle ¢ --+ ~). On reaching
H = =
Hfi M(2A + a + b), the vectors Ml and M2 flop (¢ = ~) and the
vector L goes to zero.
It thus follows from the foregoing analysis that with the field H being
parallel to the anisotropy axis, an orientation transition is possible that consists
of a rotation of the vector L from the z axis to the x axis. No such transition
is realized in the case of H J.. z. For all values of fields H the vector L remains
directed along the z axis. The question arises of how the system will behave for
an arbitrary field H direction and what the value will be of the critical angle
'1jJcr at which an orientation transition is still possible [24,25].
We eliminate the variable ¢ in the equations of state (20.40). This gives
the relation between the angles 8 and the components Mz and Hx [25]:
(;~ - ~, -cos 2'1jJ) sin 28- (sin 2'1jJ-2;~ ~, sin 28) cos 28 = ~ sin 2'1jJ, (20.45)
where A' = 2A + b. In finding '1jJcr, we may restrict ourselves to fields H ~

H o. Then terms of order t and '1jJmax '" t (t ~ 1) will play a leading role
in equation (20.45). Allowing for these conditions, equation (20.45) may be
brought into the form [25]
2Hz Hx cos 28 - [HJ - H; (1 + ~,)] sin 28 = 2 ~, HJ sin 28 cos 28. (20.46)

We differentiate equation (20.46) with respect to the angle e. Using the ex-
pression obtained, we may eliminate the angle e from equation (20.46). As a
result, we obtain the equation for Hz and Hx:
2/3 a )] 2/3 a ) 2/3

(2HzHx) + [2
Ho -
2(
Hz 1 + A' = ( 2Ho A' . (20.47)
The resulting equation determines two astroids on the (x, z) plane (Fig. 5.24).
Substitution of Hx = 0 into equation (2.47) yields the expression (20.44) for Hl
and H 2 . Over the field intervals enclosed within the astroids, an orientational
first-order phase transition is possible in which the vector L rotates from the z
axis to the x axis. The maximal angle at which such an orientation transition
is possible is determined by the critical point of the astroid [25] and is equal to
7/Jcr = 2~'
-f--------+-------l---::- Ii j.
HS1 ,}(
Fig. 5.24. Critical points on the (Hz, Hx) diagram.
The ellipse on the critical-field diagram (Fig. 5.24) determines the values
of Hsf at which a 'spin-flop' transition takes place. The major and minor ellipse
semi-axes are found from the stability conditions (20.43) and are equal to
Hsfx~M(2A+a+b),
, ,
Hsfz~M(2A-a+b). (20.48)
The determination of critical fields in anti-ferromagnets with allowance

for the Dzyaloshinsky interaction, the dependence of magnetization on the
magnitude and direction of field H, and other aspects of orientational phase
transitions have been treated in [26-28].
186 CHAPTER 5
References
1. Yu.M. Gufan, and V.P. Sakhnenko: Fiz. Tverd. Tela 14, 1915 (1972).
3. Yu.M. Gufan: Termodinamicheskaya Teoriya Fazovykh Perekhodov (Ther-
modynamical Theory of Phase Transitions), Izdat. Rostov. Univ. (1982).
4. A.P. Minina, and N.V. Proskuryakov: Vysshaya Algebra (Higher Algebra),
Fizmatgiz (1962).
5. Yu.M. Gufan, V.P. Dmitriyev, V.P. Popov, and G.M. Chechin: Fiz. Tverd.
Tela 21,554 (1979).
6. Yu.M. Gufan, V.P. Dmitriyev, V.P. Popov, and G.M. Chechin: Fiz. Met.
Metalloved. 27,787 (1979).
7. Yu.M. Gufan, and E.S. Larin: Izv. Akad. Nauk SSSR, Ser. Fiz. 43, 1567
(1979).
8. K. Aizu: Phys. Rev. B 23, 1292 (1981).
9. V.E. Yutkevich, B.N. Rolov, and A.I. Medovoy: Czechoslovak J. Phys. B
31,77 (1981).
11. K.S. Aleksandrov, A.T. Anistratov, B.V. Beznosikov, and N.V. Fedoseeva:
Fazovye Perekhody v Kristallakh Galoidnykh Soedinenii ABX3 (Phase Tran-
sitions in Crystals of Halide Compounds ABX3 ), Nauka (1981).
12. E.M. Lifschitz: Zh. Eksp. Teor. Fiz. 14, 353 (1944).
13. I.F. Lyuksyutov, V.L. Pokrovskii, and D.E. Khmel'nitskii: Zh. Eksp. Teor.
Fiz. 69, 1817 (1975).
14. N.P. Grazhdankina: Uspekhi Fiz. Nauk 96,291 (1968).
15. V.E. Naish, Yu.N. Skryabin, and V.N. Syromyatnikov: Fiz. Met. Met-
alloved. 52, 1147 (1981).
16. V.L. Indendom: Kristallografiya 4,619 (1959).
17. Yu.A. Izyumov, F.A. Kassan-Ogly, and V.E. Naish: Fiz. Met. Metalloved.
51,500 (1981).
18. X. Convent, and N.M. Plakida: Acta Phys. Polon. 63,779 (1983).
19. M. Hikada: J. Phys. Soc. Japan 39, 180 (1975).
20. N .M. Plakida, A. Podolska-Strycharska, and V. Sikora: Kristallografiya 85,
2189 (1983).
21. H. Horner, and C.M. Varma: Phys. Rev. Lett. 20, 845 (1968).
22. K.P. Belov, A.K. Zvezdin, A.M. Kadomtseva, and R.Z. Levitin: Orient-
atsionnye Perekhody v Redkozemel'nykh Magnetikakh (Orientational Tran-
sitions in Rare Earth Magnetics), Nauka (1979).
23. L. Neel: Izv. Akad. Nauk SSSR, Ser. Fiz. 21, 890 (1957).
24. S. Foner: Phys. Rev., 130, 183 (1963).
25. G.K. Chepurnykh: Fiz. Tverd. Tela 10, 1917 (1968).
26. I.E. Dikshtein, V.V. Tarasenko, and V.G. Shavrov: Zh. Eksp. Tear. Fiz.
67,816 (1974).
27. V.A. Lvov, and D.A. Yablonskii: Fiz. Niz. Temp. 8, 951 (1982).
28. V.G. Bar'yakhtar, A.N. Bogdanov, V.T. Telepa, and D.A. Yablonskii: Fiz.
Tverd. Tela 26, 389 (1974).
CHAPTER 6
Macroscopic Order Parameters
21. Transformation Properties of the Order Parameters
PHYSICAL REALIZATION OF THE MACROPARAMETERS
Every phase transition in the crystal is accompanied by the appearance at the

phase transition point Te of a whole set of physical quantities that are absent
in the initial phase. These quantities may be divided into two major groups:
microscopic and macroscopic parameters. Examples of microscopic parameters
are atomic displacements or atomic spins arising at the phase transition point
T e , and also variations of the probability of finding an atom of a given species
on a given site. It is these quantities that were treated in the previous chapters.
In addition to the parameters enumerated, a variety of physical properties
of the crystal are described by macroscopic variables, which include polariza-
tion vector or crystal magnetization components, strain tensor components,
etc. Measurement of these quantities underlies the various experimental tech-
niques of investigating phase transitions in crystals. The latter circumstance
determines the importance of studying the behavior of macroscopic variables in
the vicinity of the phase transition. Along with these conventional characteris-
tics, a great deal of attention has recently been given to macroscopic properties
described by higher-rank tensors. For example, piezomagnetic and piezoelec-
tric properties are described by components of a tensor of third rank, elastic
constants as well as electron and magnetostrictive constants by components of
a tensor of fourth rank, the quadratic piezoelectric effect, the influence of an
electric field on elastic constants and some other effects by components of a
tensor of fifth rank.
Of the entire set of different variables arising at the phase transition point,
only one is evidently a vrai (genuine) order parameter, sometimes called [1] a
primary order parameter. The transformation properties of the primary OP
188
MACROSCOPIC ORDER PARAMETERS 189
should describe an observed symmetry change at a phase transition and ob-

served anomalies in physical properties. The rest of the parameters will be
called secondary OP's [2]. The secondary parameters, too, should describe
anomalies observed in physical properties, but they may give an incomplete
description of a change in symmetry. For example, spontaneous atomic dis-
placements from equilibrium positions may be chosen as the primary OP for
the m3m -+ 4mm transition in BaTi0 3 . This transition is accompanied also by
a tetragonal crystal lattice distortion, which may be viewed as a secondary OP.
If we now analyze the crystal symmetry change at the phase transition by the
standard procedures (§8) based only on the transformation properties of the
secondary parameter, the symmetry group of the new phase will be 4/mmm
[1]. In most of the cases, macroscopic quantities specifying a phase transition
belong to secondary OP's.
We consider the transformation properties of macroscopic OP's. A knowl-
edge of these properties is indispensable, first, for one to be able to determine
from the symmetry of the initial and final phases, which of the macroscopic
quantities, absent in the initial phase, may appear spontaneously in the dissym-
metric phase. Second, in those cases where the macroscopic parameters pertain
to secondary OP's, a knowledge of their transformation properties is needed
for determining the type of their interaction with the primary OP's. Finally,
in constructing thermodynamic potentials, it is necessary for one to be able
to construct from components of macroscopic tensors, polynomials invariant
under the symmetry group of the initial phase.
All the three problems enumerated above for tensors of first order ~ vector
parameters) and tensors of second order (strain tensor) were investigated in
detail by various authors [2-4] and the results have been tabulated. For higher-
rank tensors, whose properties, as stated in the foregoing, have recently begun
to be intensively investigated, the corresponding tables are currently under
development. In what follows we briefly formulate the main principles of solving
the three problems stated.
Let Dv be a vector representation that describes the symmetry of a polar
vector (tensor of rank one). A tensor of rank r transforms as the product of r
vector components and its transformation properties are therefore described by
the tensor representation Dr rv == Dv X Dv X ••• X Dv. The crystal's physical
characteristics of interest are described by tensors that are symmetric with
respect to permutations of some indices. The most commonly used tensors are
presented in Table 6.1.
190 CHAPTER 6
Table 6.1
List of tensors frequently used in phase transition theory [2]
Tensor . Physical meaning of components

representatiOn
Dv Polarization Po:
DV Magnetization Md
Strain f. 0I{3
[D~] Stress uo:{3
Susceptibility Xo:{3
Dv[D~] Piezoelectric coefficients dill
DV[D~] Piezomagnetic coefficients BAil
[[D~F] Elastic coefficients CAll

[D~j2
Electro- and magnetostriction
coefficients
Quadratic piezoelectric effect QillV
Effe<;t of electric field

on elastic constants
Notation: [D~], second-rank tensor symmetric with respect to two

indices; Dv [D~], third-rank tensor symmetric with respect to two
indices of the three; [D~j2, fourth-rank tensor symmetric with respect
to the first pair of indices and with respect to the second pair.
The tensors summarized in Table 6.1 are said to be material [2], as they
specify properties of specific crystals and therefore depend also on the symme-
try of these crystals. Since material tensors describe macroscopic properties
of crystals, we may in our further reasoning restrict ourselves to the crystal-
lographic point groups and their IR's. The requirement that the components
of the material tensor be invariant under the crystal symmetry point group
determines the form of this tensor. Consequently, in order to determine what
microscopic variables are likely to arise spontaneously at the phase transition,
we need to find the form of the corresponding material tensor in the initial and
final phases.
A tensor invariant under the point group CO may be obtained by averaging
over the group. The gist of the method is expressed by the formula
1
(A)a o = IIcoll h~O hA, (21.1)
where A is a complete tensor of specified rank with all the components being
non-zero. As an example, we wish to find the symmetric form of the strain
tensor for the group C2h(~)' This group consists of the elements
f(XYZ), C 2z (xyz), I(xyz), mz(xyz),
where the brackets specify the transformation of the radius vector r = (xyz)
n
components for each element. The formula (21.1) then gives
:::) + ( :::
fzz -fzx
fxy
fyy
- f zy
=:::)]
fzz
= (:::
0
:::
0
(21.2)
Suppose now that an Oh(m3m) -+ C2h(2/m) transition takes place. The strain
tensor, which is symmetric under the group Oh, has the form: (f)Oh = hxx,
where I is the identity matrix. On comparing (f)Oh and (f)c2h (21.2), we see
that the Oh -+ C2h transition should be accompanied by the occurrence of
spontaneous deformation f xy .
CONSTRUCTION OF BASIS FUNCTIONS
To determine the type of the interplay of macroparameters with microparam-

eters, and also the type of the contributions that macroparameters make to
thermodynamic potentials, a group theoretic analysis is required. Just as in the
case of microparameters, such analysis should involve determining the consti-
tution of the tensor representation, computing the basis functions, and finding
the IRBI.
To start with, we describe a procedure of constructing basis functions from
the components of a material tensor of rank r. As an example, we consider the
strain tensor (r = 2). According to Table 6.1, this tensor transforms according
to the representation [D;]. The character of this representation is expressed in
terms of the character of the vector representation by the formula
(21.3)
Using this formula and tables of space group IR's for the wave-vector", =
o (these IR's coincide with the representations of the corresponding point
groups), we can readily find the constitution of the tensor representation, for
example, for the group Oh:
(21.4)
192 CHAPTER 6
Indicated in the brackets are the frequently used notations of the point group
representations. For the representations Tl, 1"5, and T7 the tensorial basis func-
tions can now be found by the projection operator method. Proceeding from
the general formula (21.1), we write the expression for the basis functions ¢'5.
transforming by the IR of the point group Co:
(21.5)
with ¢ some starting function and Il a fixed subscript.

At the outset we construct the basis function for the one-dimensional iden-
tity representation Tl(Alg). Since this representation is an identity representa-
tion, we have Ttl (h) = 1 for any h E Oh. We choose ixx as the starting function.
Then the operation of the elements h E Oh on ixx leads to a replacement of x
by y and z without reversal of sign. As a result, we obtain
(21.6)
Similarly, we obtain the basis functions for the two-dimensional Ts(Eg) and
three-dimensional T7(T2g ) IR's of the group Oh:
¢I' = V3( ixx - iyy), ¢~' = (2i zz - ixx - iyy);

(21.7)
¢? = i xy , ¢~7 = iyz, ¢;7 = i xz .
A complete list of basis functions constructed from polar and axial vector com-
ponents and second-order tensor components is presented in Table 6.2.
CONSTRUCTING THE THERMODYNAMIC POTENTIAL
Neither the straightforward method of constructing the thermodynamic po-

tential nor the method of constructing the potential from IRBI elements, de-
scribed in detail in Chap. 4, depends on the physical content of the variables
from which invariants are constructed, so the case of macro parameters is in no
way prominent in technical terms. From a physical standpoint, two situations
may be singled out. First, macroscopic parameters may be viewed as OP's for
a whole class of transitions. These are what is known as proper transitions
(see also §22). Second, as has already been stated, it is of practical interest to
analyze the secondary parameters which, as a rule, describe macroscopic prop-
erties of crystals for every single transition except for the vrai, i.e., primary
parameter. In the case of proper transitions two notations are employed in the
Table 6.2
Macroscopic basis functions constituted by polar (r) and axial (S)
vector components and by second-rank tensor for point group IR [5].
G IR Basis functions G IR Basis functions

Ci T2(A.) x,y,Z. C4h T2(Au) z.
C2 T2(B) X, y, Sx, Sy, fxz, f yz . T5(Bg) fxx - fyy, fxy
Cs T2(A") z, Sx, Sy, fxz, f yz · T3 + 1"7 (Sx, Sy), (fxz, f yz ).
C 2h T2(Au) z. (Eg)
T3(Bg) Sx,Sy,fxz,fyz . T4 + T8 (x, y).
T4(Bu) x,y. (Eu)
D2 T2(B3) X, Sx, f yz . D4 T2(A 2) z,Sz.
T3(B 2) y,Sy,fxz ' T3(BI) fxx - fxy
T4(Bt) z, Sz, f xy . T4(B 2) f xy ·

C 2v T2(A 2) Sz,fxy . T5(E) (x, y), (Sx, Sy),
T3(B2) y,Sx,fyz . (fyz, -fxz ).
T4(BI) X,Sy,fxz . C4v T2(A 2) Sz
D2h T3(B3g) Sx,fyz . T3(BI) fxx - fyy
T4(B3u ) x. T4(B 2) fxy
T5(B2g ) Sy, f xz . T5(E) (x, y), (Sy, -Sx),
T6(B 2u ) y. (fxz,fyz )
T7(B1g) Sz,fxy . D2d T2(A 2) Sz
T8(B 1u ) z. T4(BI) fxx - fyy
C4 T2 + T4 (x, y), (Sx,Sy), T3(B2) z, fxy
(E1 + E2) (fxz, f yz ). T5(E) (x, y), (Sx, -Sy),
T3(B) fxx - fyy, fxy (fyz,fxz )
S4 T2 + T4 (x,y),(Sy,Sx),
(E1 + E 2) (fyz,fxz).
T3(B) Z, fxx - fyy, fxy
194 CHAPTER 6
Table 6.2 continued
D4h T3(A 2g ) Sz, D3d T3(A 2g ) Sz

T4(A 2,,) z, T4(A 2,,) z
T5(B 1g ) fxx - fyy T5(Eg) (Sx,Sy), (fyz, -fxz ),

T7(B2g ) fxy (f xx - fyy, -2fxy )
T9(Eg) (Sx, Sy), (fyz, -f xz ) T6(E,,) (x, y)
TlO(E,,) (x, y) C6 T3 + T5 (2fxy , fxx - fyy)
C3 T2 + T3 (x, y), (Sx, Sy) (E 1)
(E) (fxx - fyy, -2fxy ), T2 + T6 (x, y), (Sx, Sy),
(fxz,fyz) (E2) (f xz , f yz )
C3i T2(A,,) Z C3h T2(A") z
T3 + T5 (Sx,Sy), (fxz - f yz ) T4 + T6 (x, y), (2fxy , fxx - fyy)

(Eg) (f xx - fyy, -2fxy ) (E')
T4 + T6 (x, y) T3 + T5 (S;r;,Sy), (fxz, f yz )
(E,,) (E")
D3 T2(A 2) z,Sz C6h T2(A,,) z
T3(E) (x, y), (Sx, Sy), T5 + T9 (2fxy , fxx - fyy)

(f xx - fyy, -2fxy ), (E1g)
(fyz, -fxz ) T3 + T11 (Sx,Sy), (fxz, f yz )
C3v T2(A 2) Sz (E2g)
T3(E) (x, y), (Sy, -Sx), T11 + T12 (x, y)
(2fxy , fxx - fyy), (E 2,,)
(fxz, f yz )
Table 6.2 continued

D6 T2(A2) z,Sz Th T3 + T5 ( V3( fxx - fyy),
T5(E1) (x,y),(Sx,Sy), (Eg) 2fzz - fxx - fyy)

(fyz, -f xz )
T>;(Tg) (Sx,Sy,Sz),
T6(E2) (2fxy , fxx - fyy)
(fyz, txz, f xy )
C6v T2(A 2) Sz
Ts(Tu) (x,y,z)
T5(Et) (x, y), (Sy, -Sx),
0 T3(E) (V3( fxx - fyy),
(fxz,fyz)
2fzz - fxx - fyy)
T6(E2) (f xx - fyy, - 2f xy )
T4(T2) (tyz, fxz, fxy)
D3h T3(A~) Sz
T4(A~) z T5(Tt) (x, y, z), (Sx, Sy, Sz)
T5(E') (x,y), (2fxy ,fxx - fyy) Td T3(E) ( V3( fxx - fyy),
T6(E") (-Sy, Sx), (fxz, f yz ) 2fzz - fxx - fyy)
D6h T3(A2g ) Sz T4(T2) (x,y,z)

T4(A 2u ) z (fyz, txz, fxy)
Tg(E 1g ) (Sx,Sy),(fyz,-fxz ) T5(Tt) (Sx,Sy,Sz)
TlO(E1u ) (x, y)
( V3( fxx - fyy),
Oh T5(Eg)
Tl1(E2g ) (2txy, txx - fyy)
2fzz - txx - tyy)
T T2 + T3 ( V3( fxx - fyy),
T7(T2g ) (fvz, fxz, fxv)
(E) 2fzz - fxx - fyy)
Tg(T19 ) (Sx,Sv,Sz)
T4(T) (x, y, z), (Sx, Sy, Sz),
TlO(Tlu) (x,y,z)
(tyz,fxz,fxy)
The IR's are denoted according to Kovalev (with", = 0) and

Landau and Lifschitz [14]; the z axis is directed along the higher-
order symmetry axis.
196 CHAPTER 6
literature, depending on whether the material-tensor components themselves

or their symmetrized combinations that transform according to the IR of the
point groups are used as the variables. To illustrate this, we choose as the
variables the strain-tensor components:
and construct a potential that is invariant under the group Oh. In this case
the straightforward method is the more convenient. We construct the various
quadratic combinations from the variables f;:
6
<1> = L rit:; + L rijf;fj. (21.8)
;=1 ;j
On operating on <1> with the generators I, C4z , C3 (111) of the group Oh and
requiring the invariance of <1>, we obtain
Proceeding similarly, we may obtain the cubic contribution
<1>(3) = V1 (f1 + f2 + (3)3 + V2( f1 + f2 + (3)( f1 f2 + f1 f3 + f2(3)+

+V3( f1 + f2 + (3)( f~ + f~ + f~) + V4f1 f2f3+
+VSf4fSf6 + V6[f1(f~ + f~) + f2(d + f~) + f3(f~ + fD]. (21.10)
Another way of constructing the same potential is by using the IRBI tech-
nique. As shown in the foregoing, the symmetrized combinations of the quan-
tities fi transform according to the group Oh IR's T1, TS, and T7. From these
representations we can construct the direct sum T1 EEl TS EEl T7. The corresponding
I group is one of the cubic groups and contains twenty-four elements specified
by the six-dimensional matrices of the reducible representation T1 EEl TS EEl T7.
Exploiting the theorems of §12, the IRBI can be constructed from the variables
4>?, {4>?,4>;5}, {4>~7,4>;\4>;7} given by the formulas (21.6) and (21.7). The
expressions (21.9) and (21,10) may then be transcribed into
(21.11)
<1>(3) = vl4>~; + v24>?(4)~~ + 4>;~)+

+V34>? (4)~; + 4>;; + 4>;;) + v44>;5 (4);5 (4>;; - 34>~;) + vs4>? 4>;7 4>;7 +
+vdJ34>r5(4);; - 4>~;) + 4>;5(24);; - 4>~; - 4>;;)], (21.12)
where the underlined terms are IRBI elements.

If, for example, we wish to explore the Oh -+ D4h transition, it suffices to
restrict our attention to the variables 4>r5 and 4>;5, which transform according
to the representation 75, and the form of the thermodynamic potential will
coincide with that obtained in §13.
In those cases where macroparameters are secondary OP's (and this is
always so at transitions with"" =P 0), the thermodynamic potential should
be constructed according to the following scheme. Isolate the initial-phase
space group IR D"Y responsible for the transition. Find the initial-phase point
group IR (or the representation of the space group with"" =P 0) according to
which the secondary variables of interest transform. Construct the reducible
representation D"Y EB D"=o and find, from the matrices of this representation,
the I group and the relevant IRBI.
22. Interplay of Micro- and Macroparameters
CONSTRUCTING THE THERMODYNAMIC POTENTIAL
We consider the scheme of constructing potentials when there are two param-
eters (in the general case these are multi component parameters). Assume that
one of these parameters is microscopic and its transformation properties are de-
scribed by space group irreducible representations, whereas the other parameter
is macroscopic and its transformation properties are described by point group
irreducible representations.
In constructing the potential, we may encounter two cases, namely: the
micro- and macroparameters may have similar and different transformation
properties. We label the microscopic OP components by 1}).., and the macro-
scopic OP components by Xa or Xi (Xa = Pa , M a , Xi = fi)' The thermo-
dynamic potential will contain two terms quadratic in the parameters 1}).. and
Xa: Tl L).. 1}~ and l{ La x~. In keeping with Landau's theory (§1) it will be
assumed that only Tl and l{ depend on temperature: Tl = T10(T - Tel), l{ =
l{o(T - Te2)' The form of the other terms involved in the thermodynamic
potential is determined by the form of the invariants contained in the corre-
sponding IRBI. To find this IRBI, we need to construct the reducible represen-
tation D"Y EB D"=o according to which the variables 1}).. and Xa transform and
to proceed henceforth in keeping with the recommendations outlined in §12.
The thermodynamic potential obtained as a result of the relevant computations
198 CHAPTER 6
may be represented as
(22.1 )
<1>7] = E 1]~ + (1]~) + (1]1) + ... ,

rl <1>7] <1>7] (22.2)
>.
<l>x = E x~ + x (X;) + ... ,

f{ (22.3)
'"
(22.4)
or in simplified form:
(22.5)
Here gl (1]) and g2 (1]) are polynomials relative to the components of the para-
meter 1], and since 1] should not transform according to the identity represen-
tation, this would imply the absence of a transition; the first term involved in
the polynomial g2(1]) is quadratic in 1].
As a rule, the outlined procedure of constructing the IRBI from the vari-
ables 1]>. and x'" is somewhat laborious to realize in practice. On the other
hand, in most of the cases one can restrict oneself to the first terms in <l>int, so
a simpler approach may be used in the construction. The gist of this approach
is as follows. It is necessary to find the least degree n such that the decomposi-
tion of the representation (DI<v)n into irreducible representations contains the
representation DI<=o. Then the terms describing the coupling of the parameters
1]>. and x'" in the potential <l>int will have the form 1]).. X",.
IMPROPER TRANSITIONS
The presence of a coupling between the parameters 1]>. and X", is responsible for
the occurrence below the phase transition point of new macroscopic properties,
which are described by quantities x",. Such transitions are normally referred
to as improper (§27). In recent years these transitions have been investigated
extensively in connection with their utilization in instrument engineering. Our
goal is to determine the form of the simplest potential describing an improper
transition. We start by considering the case when the quantities 1]>. and x'" are
one-component micro- and macroparameters. Depending on the transforma-
tion properties of these parameters, their coupling may be described by terms
of the form 1]X, 1]2X, 1]X2, 1]2x2. An interplay of the form 1]X occurs when the
parameters 1] and x transform in the same way. Such transitions are said to be
pseudo-improper [6]; they will be treated separately in §27. A coupling of the

form 7] 2 X occurs in those cases where the quantity x itself is an invariant under
the initial-phase symmetry group and therefore this type of coupling may not
be applied to describe improper transitions. The rest of the coupling types
are quadratic in the parameter x, so the case of a one-component parameter
7] is not suitable for describing an improper transition specified by a linear
interaction with respect to the macroscopic variable xc>'
A simple potential suitable for the description of improper transitions may
be constructed under the assumption that the microscopic parameter incorpo-
rates two components: '11 = (7]1,7]2). If the transformation properties of the
variables 7]1 and 7]2 are such that the product 7]17]2 transforms either as a polar
or axial vector component or as a strain tensor component, the simplest model
potential for improper transitions may be written in the form
A potential of this kind has been investigated in detail in [6].
EXAMPLES OF STRUCTURAL TRANSITIONS IN PEROVSKITE-TYPE CRYSTALS
In KMnF 3 , CsPbBr3, and CsPbCh crystals a sequence of two structural tran-

sitions (see §20) is observed. One of the structural transitions is described by
the modes of the Brillouin zone point M (star {,dl}), the other by the modes
of the point R (star {,..I3}). In KMnF 3 first a transition over the star {,d3}
(Tel = 19lK) takes place and then a transition over the star {,..II} (Tc2 = 90K)
occurs. In the compounds CsPbBr3 and CsPbCl3 an inverse sequence of struc-
tural transitions is observed: As the temperature is lowered, first the modes of
the point M ({,..II}) soften and then the modes of the point R ({,..I3}) do.
In either case the sequence of structural transitions may be described by one
potential of the form
<1>1) = r2( 7]r + 7]5 + 7]~) + U1'1 (7]{ + 17i + 7]j)+

+u21)(7]I7]5 + 7]I7]~ + 7]57]~) + v1)(7]~ + 7]~ + 7]~), (22.6)
<1>~ = r1(a + ~i + 7]~) + U1~(~t + ~i + ~i)+

+u2~(a~5 + ~I~~ + ~~~D + v~(~~ + ~~ + ~~), (22.7)
<1>'1~ = 11(7]i~I + 7]~~~ + 7]~~~)+

+/2(~i(17~ + 7]~) + ~~(7]i + 7]~) + ~~(7]i + 7]D), (22.8)
200 CHAPTER 6
where the parameters 1J>. describe the transition at the point M and the para-
meters 6 the transition at the point R [7]. In the examples considered, the
first structural transition in CsBrCla and CsPbCl3 is a first-order transition,
so it is necessary in the potentials (22.6) and (22.7) to allow for the sixth-
order terms in the parameters 'fJ>. and 6. In the following we analyze only
a particular approach rather than the entire phase diagram and therefore, to
simplify calculations, not all of the invariants of degree six will be taken into
account in the expansions (22.6)-(22.8). Having the potential (22.6)-(22.8),
one can study interaction effects of two structural transitions. We concentrate,
however, on the effects of the interplay of the micro- and macroparameters in
the vicinity of one of the structural transitions.
An important role in the investigation of structural transitions attaches to
ultrasonic measurements since analysis of ultrasound velocity anomalies pro-
vides information on the behavior of the OP's. For such experiments to be
described theoretically, it is necessary to add to the potentials (22.6)-(22.8)
the terms specifying the elastic energy of the crystal:
<Px = !CPl (xi + x~ + x~) + CP2(XIX2 + XIX3 + X2X3)+

+~Cg4(X~ + X~ + x~) (22.9)
and the interaction energy of the strain tensor with the OP [7]:
<P X 7]{ = Ol(xl1JI + X21J~ + x31JD+

+02[Xl(1J~ + 1J5) + X2(1J5 + 1Ji) + x3(1JI + 1J~)]+
+03(Xld + X2e~ + x3e5)+
+04[Xl (e~ + e5) + X2(e5 + en + x3(ei + e~)]+
+05(X466 + x566 + x666), (22.10)
Xi being the standard notation of the strain tensor components (§21). The
expression (22.10) is easy to construct with the help of the straightforward
method described in §11.
Consider the first structural transition described by the modes of the point
M ({,d I}). The symmetry group of the dissymmetric phase, according to [7],
is D~h' These data suffice to determine the solution type (0 0 1J) corresponding
to the 0]; ---+ D!h transition. Interested in this particular transition only, we
write by virtue of the formulas (22.6)-(22.10) the effective potential
(22.11)
or, on eliminating the variables Xi from the condition /

o~ OXi = 0, the potential
(22.12)
, (CP1 + CP2)8i + 2CP18~ - 4CP2 8182

(22.13)
u 1'7 = U1'7 - 2(CP1 + 2CP2)(CP1 - CP2)
A potential of type (22.12) has been explored in detail in §16, where it
is shown that in the case ui'7 < 0, the equation of state allows a solution
describing a first-order transition. The transition temperature Tc2 and the OP
jump at Tc2 are described by the expressions
( u' )2
T. - TO
c2 - c2
+ 4_1_'7 _
' (22.14)
r20 v'7
,
il'TJ = 'TJ. IT=T
U1'7
c2 = -2;"". (22.15)
'7
Using these results, we can readily calculate the anomalies of the elastic moduli
at the transition point by the formula [8]
(22.16)
~ _ ( 02~eff )
(22.17)
)../-1 - O'TJ)..O'TJ/-I •.
As a result, we can write the values of the elastic moduli above the tran-
sition temperature (T > TC2):
Cij = C~ (22.18)
and below the transition temperature (T < Tc2):

C 11 = CP1 - 8~(2u1'7 + 6V'7'TJ;)-1, C 12 = CP2 - 8~(2u1'7 + 6v'7'TJ;)-1,
(22.19)
C33 = cg3 - 8i(2u1'7 + 6V'7'TJ;)-1, C44 = cg4.
The temperature dependence of 'TJ. can be determined from the condition
8~eff/O'TJ. = 0. On replacing 'TJ. by il'TJ, we obtain the jumps of the elastic
moduli at the phase transition point. The second structural transition can be
described in a similar way.
By comparing the derived temperature dependences of moduli Cij with
experimental data obtained from measurements of sound velocity anomalies,
we can obtain information about the phenomenological parameters involved in
the potential (22.6)-(22.10).
202 CHAPTER 6
23. Ferroics
CLASSIFICATION OF DISSYMMETRIC PHASES ACCORDING TO MACRO-

PROPERTIES
The previous chapters were concerned with different aspects of the symmet-
ric and thermodynamic description of phase transitions, based on an analysis
of the transformation properties of the macroscopic OP's. In particular, we
have ascertained (§9) that the crystal symmetry lowering at a phase transition
leads to the formation of a domain structure from which rotational, arm, and
translational domains may be singled out. The presence of rotational and arm
domains is due to a decrease in rotational crystal symmetry and the presence
of translational domains is associated with a change in translational symmetry.
Correspondingly, all the phase transitions may be broken up into two types.
The first type includes transitions in which the dissymmetric-phase point group
G~ does not coincide with the initial-phase point group GO (G~ C GO). The
second type comprises transitions for which the point groups of the initial and
dissymmetric phases coincide (G~ = GO). Crystals that undergo transitions
of the first type are often said to be ferroics [9]. Because of the lowering of
the point symmetry, the dissymmetric phase in ferroics should be described by
macroscopic variables, alongside the microscopic OP's. For example, if there
occurs in the crystal a phase transition with tl, = 0 from an initial cubic-
symmetry phase to a tetragonal dissymmetric phase, then the dissymmetric
phase should consist of three domains. Each domain differs from the other in
the strain tensor describing the spontaneous deformation of the parent cubic
cell along one of the edges x, y, z. The physical nature of the spontaneous mi-
croscopic variable arising at the phase transition underlies the classification of
crystals that undergo phase transitions. Thus materials in which a spontaneous
polarization or magnetization vector occurs at a phase transition are called fer-
roelectrics or ferromagnetics. A crystal in which the dissymmetric phase is
described by the spontaneous strain tensor is called a ferroelastic. Similarly,
other types of ferroics are distinguished. A crystal classification based on these
principles is presented in Table 6.3. To determine to which item of Table 6.3 a
particular phase transition GO -+ G~ belongs, we need to find the point group
GO representation D V describing the symmetry change GO -+ G~ and then
to calculate the basis functions of this representation from the material tensor
components. If the basis functions can be constructed from the polarization
vector components, we have a ferroelectric transition. But if the non-zero basis
Table 6.3
Classification of ferroics [10]
lVlacrgv.anables
Type of ferroic shecI ylllg DO,I)1~in Examples
t e domams SWItC over field
Spontaneous
Eerro~
electrIC polarization ~~ratric BaTi0 3
EerrQ- Spontaneous Nechanical f3 - AUxCul_xZn

elastIC strain s resses
Ferro- . Sponta~e0l!s Ma£netic Fe304
magnetIc magnetIzatIOn fiel
h~~O- DielectJ:~.. ~~ratric
Ie ectric susceptl Ihty
h~rro- . Magnetic Ma£netic NiO
ImagnetIc susceptibility fiel
h~ItO- Elasticity Mechanical Si0 2
Ie astic coefficients stresses
Eerro- . I}iezo~ ~lr~ric

e or.
elastoelectrIc e ecg,IC
coe clents ::lec amcal
s resses
Ferro- . Piezo- . Ma!etic

magnetoelastIc maWietIc fiel or. CoF 2
coe cients rrec amcal
s resses
Magneto- Ma£netic
Ferro- . eleW,ic ~el Qr Cr 2 0 3
magnetoelectnc coe Clents fi~<Jnc
functions of the representation DV are constructed from the components of a

polar tensor of rank four, the phase transition is a ferrobielastic one, etc.
The experimental determination of ferroic types reduces to finding combi-
nations of external fields that switch domains over. Thus, for example, if the
domain structure is not observed in a polarized light, and the external stresses
switch the domains over, then the crystal in which this domain structure occurs
is a ferrobielastic. But if the domain structure is observed in a polarized light,
a ferroelastic transition takes place.
Ferroics in which all domains differ in spontaneous macrovariables (as was
the case in the example considered above) are said to be complete. But if not
all of the domains but only part of them have different spontaneous macrovari-
ables, then the corresponding crystal is called a partial ferroic [9]. For example,
204 CHAPTER 6
let the (Go = Oh) -+ (G~ = D 4h ) transition be accompanied by doubling of the

parent unit cell. Then six domain types should arise at the transition. These
may be broken up into three pairs. Each pair differs from the other in the
deformation of the initial cubic cell. The domains within a pair have the same
deformation and differ in shift by the corresponding translation. A crystal that
undergoes such a transition belongs to the class of partial ferroics. It should be
noted that the classification into complete and partial ferroics is based on sym-
metry principles, whereas the subdivision into proper and improper transitions
rests on the transformation properties of the parameters involved (§22).
We consider briefly the main ferroic types.
FERRO ELECTRICS
This class of ferroics has received the most study. As is seen from Table 6.3, the
macroscopic variable describing the ferroelectric transitions is a polar vector,
that is, a first-rank tensor. Since a vector transforms according to a represen-
tation of dimension not higher than three, every proper ferroelectric transition
should be described by one of the twelve thermodynamic potential types cor-
responding to the crystallographic point I groups (§14). The IRBI's of these
groups are outlined in §14.
In the case of improper ferroelectrics the procedure of constructing the
potential becomes somewhat more complicated. Namely, it is required, by an-
alyzing the relation of the space groups of the initial and final phases, to find
the relevant IR DV. Then, by analyzing the point symmetry change at the
transition, we need to find the representation D"=o describing the transfor-
mation properties of the polarization vector. The IRBI should be constructed
according to the technique (outlined in §12) for the representation D V EB D"=o.
A detailed analysis of the improper ferroelectrics which are not simultaneously
ferroelastics is contained in [11]. It has turned out that transitions of this kind
are described by three potentials:
(23.1)
where
<1>2 = r(7]r + 7]5 + 7]5) + Ul(7]r + 7]5 + 7]5)2 + u2(7]r7]5 + 7]r7]5 + 7]57]5)+
+KP2 + (8P)7]17]27]3; (23.2)
(23.3)
The first potential (23.1) describes improper ferroelectric transitions in

orthorhombic and tetragonal crystals and corresponds to different space group
two-dimensional IR's for different Brillouin zone points.
The second potential (23.2) refers to improper transitions in hexagonal
crystals over the three-dimensional IR's of the Brillouin zone point M. The two-
dimensional IR's of the hexagonal Brillouin zone point J{ lead to the potential
(23.3). By contrast with the potentials (23.1) and (23.2), this potential involves
invariants of degree six in the parameters 'T]1 and 'T]2, as among the fourth-order
invariants there are no anisotropic ones.
FERROELASTICS
The role of the macroscopic variable describing phase transitions in ferroelastics

is played by the strain tensor, which is a second-rank tensor. Ferroelastics may
be viewed as a mechanical analog of ferromagnets. Thus ferroelastics exhibit
hysteresis loops in strain-stress variables. In ferroelastics the domain structure
arising at the transition may be observed in polarized light. Table 6.4 furnishes
some examples of proper and improper ferroelastics.
A thermodynamic description and symmetry analysis of phase transitions
in ferroelastics should be carried out following the same scheme as that with
ferroelectrics. Exhaustive tables specifying the relevant IR, the I group, the
IRBI and the type of potential for each transition prescribed by the symmetry
change are available in [12].
FERROBIELECTRICS AND FERROBIMAGNETICS
By definition, ferroelectrics (ferromagnetics) and anti-ferroelectrics (anti-ferro-

magnetics) should be reckoned as belonging to the class of ferrobielectrics and
ferrobimagnetics. In ferroelectrics and ferromagnetics, however, the presence of
a spontaneous polarization and magnetization vector masks the ferrobielectric
(ferrobimagnetic) properties which should be described by the external-field-
induced polarization or magnetization vector. As already stated, one of the
experimental methods for determining the type to which a phase transition
belongs is to switch over the domains by an external field owing to the dif-
ference of the macroscopic characteristics of different domains. Thus a mani-
festation of ferrobielectric and ferrobimagnetic effects should be expected in
206 CHAPTER 6
Table 6.4
Examples of compounds undergoing a ferroelastic transition
Compounds Initial phase Dissymmetric phase Tc(I<)
Proper
V3Si O~ D~h 21
InTI O~ DI7 320
4h
KN0 2 0 9h Dg d 295
TbV0 4 DI9 D24 33
4h 2h
Improper
SrTi0 3 O~ DI8 196

4h
SmAI0 3 O~ D~h 653

CuAu O~ DI6 -
2h
V0 2 DI4 C~h 343

4h
Hg 2Ch DI7 D17 185

4h 2h
anti-ferroelectrics (anti-ferromagnetics) with high anisotropy of the dielectric

(magnetic) susceptibility tensor [10].
Since the dielectric and magnetic susceptibility tensor is a second-rank
tensor, the symmetry properties of ferrobielectrics (ferrobimagnetics) should
be the same as those of ferroelastics. Thus all ferroelastics should possess also
ferrobielectric (magnetic) properties. For example, NiO is a ferroelastic, a fact
which is confirmed by a direct observation of the domain structure and by the
displacement of domain boundaries under the effect of external stresses. A
domain boundary displacement is also observed when NiO crystals are placed
in a magnetic field; this allows the NiO crystals to be referred to the class of
ferrobimagnetics.
HIGHER-ORDER FERROICS
In keeping with the above described classification of ferroics, crystals in which

the phase transitions are accompanied by the appearance of spontaneous tensor
Table 6.5
Point symmetry change types for higher-order ferroics [13]
Notation: diJj , piezoelectric tensor; C)..Jj' elasticity coefficient; L)..Jjv,
polar sixth-rank tensor
Spontaneous tensor
Ferroic type Symmetry change components
Ferroelasto-
electric mmm 222 d 14 , d25 , d36
4/m 4 d 14 , d15 , d31 , d36
4/mmm 422 d 14
4/mmm 42m d 14 , d36
3m 32 d 14 , dl1
6/m 6 d l1 , d22
Dvx[DvF 6m2 6 d l1
6mm 6 d 14
6/mmm 6 d l1 , d22
6/mmm 6m2 d 22
6/mmm 622 d 14
m3 23 d 14
432 23 d 14
m3m 43m d 14
m3m 23 d 14
Ferrobielastic 4/mmm 4/m C 16
[[D~F] 3m 3 C 15
6/m 3 C 14 , C25
6/mmm 3m C 14
6/mmm 3 C 14 , C 25
208 CHAPTER 6
Table 6.5 continued
Spontaneous tensor
Ferroic type Symmetry change components
Ferroelasto-
electric and
ferrobielastic 42m 4 d 15 , d31 , C 16
4mm 4 d14 , C 16
r
4/mmm 4 d 14 , d15 , d31 , d36 , C 16
Dv X [Dv j2 and [[DV]2 3m 3 d ll ,dI4 ,CI5
6 3 dll,d22,CI4,C25
6m2 32 d14 , C14
622 32 dll, C14
6mm 3m dll, C 14
6mm 3 dll, d22 , d14 , C14, C25
6/mmm 32 dll, d14 , C 14

Higher-order
ferroics 6/mmm 6/m L ll6 , L 145
43m 23 Lll3 - L 112 , L 166 - L 155
m3m m3 L 113 - L 112 , L 166 - L 155
m3m 432 eolar ninth-rank

ensor
quantities of rank three and higher than three belong to higher-order ferroics.
According to the nature of the spontaneous third- and higher-rank quanti-
ties, the higher-order ferroics are subdivided into ferroelastoelectrics, which
are characterized by the occurrence of spontaneous components of the piezo-
electric tensor dip, ferrobielastics, which are characterized by the occurrence of
spontaneous components of the elasticity tensor CAP' and higher -order ferroics
proper.
Just as with ferroelectrics and ferroelastics, we can enumerate all types
of point symmetry change for higher-order ferroics (Table 6.5). The left-hand
column of Table 6.5 gives the name of a ferroic and shows the physical repre-
sentation according to which the corresponding tensor components transform.
The non-zero spontaneous tensor components liable to arise at a specific phase

transition are indicated in the last column of Table 6.5.
Using Table 6.4 permits enumeration of all the space groups which the
higher-order ferroics may have. As shown in [13], there are a total of 147
such groups. An analysis of the IR's of these 147 space groups and of their
basis functions constructed from components of third-, fourth-, and higher-rank
tensors has shown (see also [14]) that proper higher-order ferroics are described
by a one-dimensional IR with;;, = 0; the point symmetry of the crystal should
lower by a factor of two, that is, IIGo"/"G~11 = 2. And improper higher-order
ferroics may be described both by multidimensional IR's with Ii, = 0 and by
IR's with Ii, =1= O.
Few specific examples are currently known of higher-order ferroics. This
is so because they are difficult to identify. Normal ferroics such as ferroelastics
are easy to identify from optical indicatrices, which are distinct for different
domains [3]. In higher-order ferroics distinct twins no longer differ in either
spontaneous strain fo:{3 or optical indicatrices and, as a result, are rather diffi-
cult to detect. For example, in the case of ferrobielastics the twins appearing
in the low-symmetry phase undergo, under the influence of external forces,
second-order effects only. That is to say, the sign reversal of the applied stress
does not reverse the direction of the domain boundary displacement [3]. This
effect was detected at the 0' - f3 transition in quartz, which is simultaneously
a ferrobielastic and a ferroelastoelectric.
We give examples of higher-order ferroics. Iron sulphide FeS is a repre-
sentative of improper ferroelastoelectrics. At T = 410K a P: /mme --+ P62e
transition occurs which is described by a six-component OP that transforms
according to an IR of the Brillouin zone point H.
A proper ferroelastoelectric transition Pm 3m --+ P43m occurs in NH 4 CI
at T = 243K.
A representative of ferrobielastics undergoing a proper transition R3e --+
R3 at T = 648K is LaCo03.
Table 6.6 presents materials that, by virtue of their structural data, may
be higher-order ferroics [13]. The principle of selecting these materials is based
on the fact that the structure of each compound may be viewed as a weakly
distorted version of a more symmetric hypothetical structure Go. The ratio
of the point groups GO and Gg should not contradict the data of Table 6.5.
The principles of searching for the groups Go are the same as those used in the
selection of the paraphase (§1O).
210 CHAPTER 6
Table 6.6
List of compounds in which one may expect phase transitions accom-
panied by spontaneous occurrence of high-rank tensors (r 2:: 3) [13]
Dissymmetric Transition
Type Compound Paraphase phase type
Ferro- K2Os02(OH)4 14/mmm 141m P

bielastics
Ash R3c R3 P
FeSiF 6 ·6H 2O R3m R3 P

Ferroelasto-
eledrics
PNb g 0 25 14/m 14 P
CuCr204 14!/amd 142d P

Cs3As 2Cl g P3m1 P321 P
N2 Pa3 P2 1 3 P
KAlO 2 Fd3m P2 1 3 I
BiF3 Fm3m P43m I

Ferroelasto-
electrics and Na2ThF6 P62m P321 P
ferro-
bielastics
Higher-order
ferroics K3 W 2Cl g P6 3 /mmc P6 3 /m P
K 2NaAlF 6 Fm3m Pa3 I
N2H6Ch Fm3m Pa3 I
Notation: P, proper transition; I, improper transition
We conclude by noting that in addition to the classification of phase tran-

sitions considered in this section, there also exist other classification methods
that are based on other principles [15]. Thus distortional ferroelectric phase
transitions and ordering-type transitions are distinguished. The distortional
ferroelectric transitions are subdivided into ferrodistortional (transitions with
n, = 0) and anti-ferrodistortional (n, :f 0) transitions, etc.
24. Non-ferroics
CRYSTAL-CLASS-PRESERVING PHASE TRANSITIONS
As stated in the foregoing, the very fact that a spontaneous macroscopic quan-
tity arises at the phase transition may, irrespective of the physical content of
this quantity, provide a basis for a classification of phase transitions. Thus the
concept of the ferroic was introduced to denote a vast class of crystalline ma-
terials in which the phase transition may be accompanied by the occurrence of
spontaneous macroscopic variables. The rest of the materials should evidently
belong to the opposite class of 'non-ferroics'.
A major group-theoretic indication of ferroics is that the point symme-
try of the crystal should necessarily change at the phase transition, as it is
the symmetry of the final and initial phases that determines the nature of
the spontaneous macroscopic quantities. Major group-theoretic indications of
non-ferroics are the obligatory preservation of the crystal point symmetry at
the phase transition and the obligatory change of the translational symmetry.
Along with the term 'non-ferroic', introduced in [16], we will therefore speak
also of a translational phase transition.
The various translational phase transitions have actually been enumerated
in tables of subgroups of space groups [17]. From these tables, it is seen that
most of the possible translational transitions are described by one-arm stars.
In the case of many-arm stars the translational transition is described by a
full-arm channel.
To describe exhaustively all potential non-ferroics, it is necessary to find
for each translational transition the relevant IR and its image (I group), using
tables [17], and to construct the IRBI. This program has been fully implemented
in [16], but only for the case of second-order translational phase transitions.
As follows from the results of that paper, the translational transitions are
comparable in number with so extensive a class of ferroics as the ferroelastics
(§23). It turns out that of the 230 space groups, 167 may be taken as the
symmetry group of the initial phase of non-ferroics. For these 167 groups a
total of 1800 possible translational transitions, described by 1713 active IR's
of sixty-five Brillouin zone points, have been revealed. Of the 1713 active
representations, 1191 IR's are one-dimensional and belong to the case of a
one-arm star. The phase transitions in these cases should be accompanied by
doubling of the primitive cell. For two-arm stars of thirteen Brillouin zone
points, 330 active IR's have been found. The corresponding transitions should
212 CHAPTER 6
be accompanied by quadrupling of the crystal primitive cell. The rest of the

cases relate to three-, four-, and six-dimensional IR's.
All the 1713 IR's are reducible to fifteen I groups: one one-dimensional
(Ci), four two-dimensional (C4V ' C4 , C6v , C6 ), two three-dimensional (Th' Oh),
five four-dimensional, and three six-dimensional representations. In analyzing
physical properties we can use nine rather than the fifteen different potentials
if, in the construction of potentials from IRBI elements for six-dimensional I
groups and the I groups C6 and C6v , we restrict ourselves to invariants of
degree six and to invariants of degree four in the other cases.
Finally, proceeding from the definition of the non-ferroics, the following
conclusions may be drawn about the behavior of the various physical properties
of non-ferroics in the vicinity of the translational phase transition. First, since
the translational transitions are not accompanied by alteration of the point
symmetry, only antiphase domains should be observed in the low-symmetry
phases. The absence of rotational domains below the phase transition point
may be an experimental indication that the compound investigated pertains
to the class of non-ferroics. Second, because of the preservation of the point
symmetry in non-ferroics, no macroscopic variables x will arise spontaneously at
the phase transition point. The various anomalies in the physical characteristics
of ferroics will manifest themselves as anomalies of the macroscopic quantities
that exist in the initial phase.
The above enumerated features of translational phase transitions make
these transitions difficult to detect experimentally. One of the factors by which
one may decide on a translational transition that has come about is the pres-
ence of superstructural reflections on neutron diffraction patterns. In this case
the reflections corresponding to the initial phase should not split up at the tran-
sition point, which is a consequence of the preservation of the point symmetry
at such transitions.
EXAMPLES OF NON-FERROICS
We conclude by enumerating some compounds that have been found to be

non-ferroics. In an ordering CU3Aul alloy a translational phase transition
Fm3m --+ Pm3m occurs at 394C. This transition is described by the IR Tl
of the group Fm3m point X. All of the three arms of the star {ldO} par-
ticipate in the transition. This same representation describes the structural
transitions in the compounds PrTe, EuS, EuSe and EuTe, in which the initial
phase Fm3m has a NaCI structure and the dissymmetric phase a CsCI struc-
ture. A transition of the type NaCI- CsCI occurs also in the compounds SmTe
and EuO, but is accompanied by an electronic transition. All of the NaCI -

CsCI type transitions may be induced also by pressure. Thus, for example, the
structural transition in EuO occurs at 400 kbar, in EuS at 215 kbar, in EuSe
at 145 kbar, etc. [18,19].
Among the representatives of the orthorhombic class, the most interest-
ing representatives of non-ferroics are compounds such as KMnF 4 [16]: KFeF 4,
KVF 4, KTiF 4. In KFeF 4, for example, a translational phase transition
Ammm -+ Amma occurs at 290°C which is described by the IR of the point
z. At 95° C the same compound exhibits one more translational transition,
Amma -+ Pmmm, which is described by the IR of the point Y. The latter
transition takes place also in KVF 4 at 255°C and in KTiF 4 at 215°C [20,21].
A translational phase transition R3m -+ R3c has been detected at 275°C
in NaN0 3; this transition is described by the representation of the point Z.
In YMn03 a cell-tripling translational transition P6 3/mmc -+ P6 3/mcm has
been detected which is described by the wave-vector Ii, = (~, - ~,O) (point
I<). This transition proves to be a first-order transition since the IR does not
satisfy the Landau condition. In AB3 type compounds (Mg3Gd and Ti3AI)
a cell-quadrupling transition P6 3/mmc -+ P63/mmc has been found to take
place. The transition is described by the IR of the point (Ii, = (~ 0 0». Just as
in the previous example, this transition is of first order since the IR is a passive
one. A more complete list of non-ferroics is given in [16].
References
1. R.A. Cowley: Adv. in Phys. 29, 1 (1980).

2. Yu.I. Sirotin, and M.P. Shaskol'skaya: Osnovy Kristallofisiki (Fundamen-
3. V.L. Indenbom: Kristallografiya 5, 115 (1960).
5. V. J anovec, V. Dvorak, and J. Petzelt: Czechoslovak J. Phys. 25, 1362
(1975).
6. M.E. Lines, and A.M. Glass: Principles and Application of Ferroelectrics
and Real Materials, Clarendon Press (1977).
7. S. Hirotsu, T. Suruki, and S. Sawada: J. Phys. Soc. Japan 43, 575 (1977).
10. R.E. Newham, and L.E. Cross: Mater. Res. Bull. 9, 927,1021 (1974).
11. P. Toledano, and J .C. Toledano: Phys. Rev. B 14, 3097 (1976).
214 CHAPTER 6
15. R. Bline, and B. Zeks: Soft Modes in Ferroelectrics and Anti-ferroelectrics,
Elsevier-North Holland (1974).
17. V.E. Naish, S.B. Petrov, and V.N. Syromyatnikov: Podgruppy Prostranst-
vennykh Grupp. II. Podgruppy s Ismeneniyem Yacheiki (Subgroups of Space
Groups II. Subgroups with Alteration of Cells), Dep. VINITI, No. 486-77
(1977).
18. A. Chattergee, A.K. Singh, and A. Jayaraman: Phys. Rev B 6,2285 (1972).
19. A. Jayaraman, A.K. Singh, A. Chattergee, and S. Ushe Devi: Phys. Rev.
B, 9 2513 (1974).
20. M. Hidaka, LG. Wood, B.M.R. Wanklyn, and B.J. Gerrard: J. Phys. C
12, 1799 (1979).
21. M. Hidaka, LG. Wood, F.R. Wondre: J. Phys. C 12,4179 (1979).
CHAPTER 7
Phase Transitions in an External Field
25. Phase Diagrams
CONSTRUCTING A POTENTIAL FOR A SYSTEM IN AN EXTERNAL FIELD
In the construction of a thermodynamic potential <P describing the influence of

an external field X on a phase transition, we should distinguish between two
situations. One of them arises when a macroscopic quantity x (for example, po-
larization, magnetization, deformation) is the order parameter. Allowance for
the external field here reduces either to adding to the thermodynamic potential
the term xX, where x is a generalized variable and X a conjugate field to it
(the equation of state then has the usual form 8<p/ax = 0), or the potential is
kept unchanged and. the equation of state becomes X = a<P / ax.
In those cases where the role of the OP is played by microscopic variables 7],
an external field X may have only an indirect effect on these variables through
their relation to macroscopic variables x conjugate to a given field X. The
thermodynamic potential in this situation is constructed in keeping with the
recommendations of §21 and the external field is introduced either in the form
of the term xX or is taken into account in the representation of the equations
of state.
The representation of the thermodynamic potential in the form of equa-
tions (22.1)-(22.5) presupposes that the variables x are independent thermo-
dynamic variables. In a number of cases it is more convenient to choose as
independent variables generalized forces X (X = E, P, H), as these quantities
are easier to vary experimentally than the generalized thermodynamic variables
x (x = P, f Oi {3, m). Since the generalized thermodynamic variables x and the
generalized forces X conjugate to them have the same symmetry, the potential
" = 1'1 L 1]~ + ,,(1]~) + <1>,,(1]1) + ... , (25.2)

A
<l>x = L LX~ +X(X~) + ... , (25.3)

or
(25.4)
The generalized variable x in this representation of the potential is described
by the expression
(25.5)
PHASE DIAGRAM FOR THE 1]4 MODEL
We illustrate the basic principles of constructing phase diagrams in terms of

the variables T, X by simple models with a one-component OP. We start with
a potential of the form
(25.6)
The coupling of the OP x to the field X is described by the equation of
state
21'x + 4ux 3 = X. (25.7)
The x(X) function for different values of l' = 1'~(T-To) is portrayed in Fig. 7.l.
Analysis of the equation of state (25.7) allows one to make a plot of the para-
meter x versus the temperature T (coefficient 1') for different values of the field
X (Fig. 7.2): The segments 3-4 and 7-6 of the x versus X curve in Fig. 7.1
correspond to metastable states. The segments 4-5 and 5-6 refer to unstable
states with negative values of the second-order derivative ({)2<1> / ()x 2 < 0) or
with a negative inverse susceptibility X- 1 by virtue of the equation
X
-1
=
({)X)
{)xs
({)2<1»
= ()x 2 s·
(25.8)
The symbol s here indicates that the corresponding quantity is taken for X = O.
Analysis of the x versus X curves sketched in Fig. 7.1 enables us to make
a plot of the potential versus the field X at T < To. This relation is shown
in Fig. 7.3.
Examination of the x(X) and (X) relations shows that as the field X is
varied, the OP x and the energy of the system should exhibit discontinuities
between the states corresponding to the points 4-8 and 2-6. A hysteresis loop
2-3-4-8-7-6 should be observed in experiment. The coercive field is equal to
HX6 - X4)'
PHASE TRANSITIONS IN AN EXTERNAL FIELD 217
,x
T>To
..X
Fig. 7.1. Field dependence of the parameter x at T> To and T < To

for the potential (25.6). The x(X) solid lines refer to stable states of
the system; the dashed lines refer to unstable states.
Fig. 7.2. Dependence of the order parameter x on temperature (r =

r~(T - To) for X > O. The solid lines refer to stable states of the
system; the dashed line refers to unstable states.
By analyzing the x(X) (Fig. 7.1) and (X) (Fig. 7.3) plots, one can con-
struct a phase diagram such as that depicted in Fig. 7.4. As can be seen from
Fig. 7.4, the kind of the phase transition changes at the point 0 (tricritical
point).
PHASE DIAGRAM FOR THE ",6 MODEL
In a variety of compounds one experimentally observes first-order phase tran-

sitions, but the transformation properties of the OP's exclude cubic invariants.
218 CHAPTER 7
9 82
Fig. 7.3. Field X dependence of the minimized potential at T < To.
Fig. 7.4. Phase diagram for the system with the potential (25.6). The
dashed line refers to second-order phase transitions; the solid line
refers to first-order phase transitions; the dot-and-dash line refers to
the stability boundary of the phases.
In describing such transitions, one allows for the invariants of degree six in-
volved in the potential and assumes that the coefficient of the fourth-order
invariant is negative (§ 16 and also [1,2]). Consider the effect of an external
field on these transitions, proceeding from the expression for the potential
(25.9)
where v > 0 and u < 0 [1].

The equation of state
2rx + 4ux 3 + 6vx 5 = X. (25.10)
enables one to make plots of the OP x versus the temperature r = rh(T - To)
and the field X, which are presented in Figs. 7.5 and 7.6. Analysis of the x(X)
and x( r) relations permits separation of three temperature intervals. The first

interval is determined by the inequality T> T cr , where Tcr is the temperature
at which an inflection occurs on the 4>(x) function. In this temperature range
the quantity x varies smoothly with varying field X (Fig. 7.5) and the phase
transition is impossible whatever the values of X.
Fig. 7.5. Dependence of the parameter x on the external field X for

the potential (25.9). The solid lines refer to stable states; the dashed
lines refer to unstable states.
x<x ,~
Fig. 7.6. Temperature dependence of the parameter x for different

values of the field X (X > 0). The solid lines refer to stable states;
the dashed lines refer to unstable states.
The second interval is given by the inequalities Tc < T < T cr , with Tc the
temperature of a first-order phase transition in the absence of a field (§16). In
220 CHAPTER 7
this temperature interval the x versus X curves display negative-susceptibility

segments which correspond to unstable states. Therefore, on reaching a certain
value of the external field X, a first-order transition will occur in the interval
Tc < T < T cr . Finally, with T < Tc the OP x undergoes a discontinuous change
in a zero field. The values of the parameters rcr and Xcr are found from the
conditions
(25.11)
which correspond to the occurrence of a point of inflexion on the CP versus x

curve. Combined with the equation of state (25.10), these two equations yield a
system for determining rcr and Xcr. from which we readily obtain the following
values [1]:
lui) 5/2
Xcr = 16v ( 5v ' (25.12)
3u 2
rcr = 5v ' (25.13)
(25.14)
To construct a phase diagram in terms of the variables z and X, we rewrite

the expression for the potential CP and the equation of state (25.10) in dimen-
sionless form, using the expressions (25.12)-(25.14):
(25.15)
15rx - 10x 3 + 3x 5 = 8X, (25.16)
_ x
X=-,
Xcr
_ r
r=-,
-
X=-.
X (25.17)
rcr Xcr
By assigning different values of the parameter X, a set of r(.X) curves can

be constructed with the help of the equation of state (25.16) (Fig. 7.7). The
expression (25.16) tells us that at small x the r versus X curve intersects the
X = 0 axis in the vicinity of the point r = O. As the parameter x is in-
creased the point of intersection of the f( X) curve with the X = 0 axis ascends
(Fig. 7.7) while the term (-10x3) involved in the expression (25.16) makes a
larger contribution than 3x 5 . Finally, at certain values of the parameter x the
contribution of the term 3x 5 becomes dominant and the point of intersection
of f(X) with the X = 0 axis starts descending. By analyzing the variation of
Fig. 7.7. Phase diagram in the variables (T, X) [3] for the 1]6 model.
The solid lines refer to the first-order transition; the dot-and-dash
lines refer to the boundaries of the regions where the phases coexist
(see Table 7.1).
Table 7.1
List of regions of existence of different phases on the phase diagram
of the 1]6 model (Fig. 7.7)
Initial
Region phase Phases Phases
BDG S M -
CDG M S -
BGF S M M
AFGC M S M
ACE - S M
Notation: S, stable phase; M, metastable phase.
the potential for each value of the parameter ii:, we can locate boundaries of
existence of the initial phase, boundaries of coexistence of several phases, and
phase transition points [3]. It is in this way that the authors of [3] found the
regions of coexistence of phases (phase stability overlap regions), delineated
by a dot-and-dash line in Fig. 7.7, and the first-order phase transition line,
222 CHAPTER 7
shown by a thick solid line. The first-order phase transition line terminates at
a critical point D with coordinates r = 1, X = 1 [3].
SINGULAR POINTS ON THE PHASE DIAGRAM
With u > 0 the critical values determined from the conditions (25.11) are
1'cr = Xcr = Xcr = O. This point is normally referred to as a central critical
point [3]. Critical points in the case of u < 0 (D-type points), the values of
which are given by the expressions (25.12)-(25.14), will be called critical points
of phase diagram wings. Assuming the parameters l' and u of the potential
(25.9) to depend on T and the external field X ext (for example pressure P), we
can construct a phase diagram in the space of T, X, X ext , where X is the field
conjugate to the OP (Fig. 7.8) [3]. The diagram portrayed in Fig. 7.7 may be
viewed as one of the cross-sections X ext =const of the diagram in Fig. 7.8. The
point t (Fig. 7.8) at which three second-order phase transition lines converge
is said to be a tricritical point. The Ft line and its continuation lie in the
(T, X ext ) plane; the surface spanning the Ft and tD lines and the surface
symmetric relative to it are the surface of first-order phase transitions.
"- '\
A \
\
\ Xed
Fig. 7.8. Phase diagram in the space of the parameters T,X, and
X ext for the 1]6 model. The dashed line represents a second-order
phase transition; the solid line shows the phase diagram section cor-
responding to Fig. 7.7.
In the (1', X ext ) plane the point t can be obtained from the condition
1'(T, X ext ) = u(T, Xexd = 0 [2].
MULTICOMPONENT ORDER PARAMETER
The foregoing exploration relates to a one-component OP. As an example of

a phase transition described by a multicomponent OP, we consider the struc-
tural phase transition occurring in A-15 compounds. Specifically, we will be

concerned with the effect of the pressure P. The structural transition taking
place in the above compounds and the symmetry analysis of this transition
have been described in §13. We said there that the compounds Nb 3Sn and
V3Si exhibit a spontaneous transformation from a cubic to a tetragonal crystal
and that this transition is accompanied by a change in symmetry: O~ --+ D~h.
The transition is described by the IR 75 of the group O~ with If, = O. Since the
translational symmetry of the crystal remains unchanged at the transition, the
strain tensor components fo:(3 may be chosen as the macroscopic variables. As
shown in §21, the strain tensor components may be used to construct the basis
functions of the two-dimensional representation 75 of the group Oh as
(25.18)
The thermodynamic potential for this representation was constructed by the

IRBI method in §13 and has the form (see equation (11.19))
(25.19)
The phase transitions corresponding to the potential (25.19) were explored in

detail in §17, where it was shown that there are three dissymmetric stable
phases which are characterized by the values of the two-component OP:
(25.20)
These three phases have the same energies, as can be readily verified by sub-
stituting the corresponding values Of'T}l and 'T}2 into equation (25.19), and cor-
respond to three different domains of the same phase, for example ('T}, 0). An
applied pressure should, however, lift this degeneracy. Indeed, we add to the
expression (25.19) the term
(25.21 )
where 0"1 and 0"2 are external forces conjugate to the OP. These quantities
are constructed on the basis of the expressions (25.19) from the strain tensor
components 0"0:(3:
(25.22)
224 CHAPTER 7
Consider the uniaxial pressure given by the expressions 0"1 = and Ts

0"2 = O.
A phase of the ('fJ, 0) type is now determinable from the equation of
state &<P/&'fJ1 = 0:
(25.23)
and a phase of the ('fJ1 'fJ2) type is determined from the system of equations of
state &<P/&'fJ1 = 0 and &<P/&'fJ2 = 0, which can be rewritten in the form
0"1 0"1
r - 3V'fJ1 + 2u(4'fJ12 - v
2 2
-3 ) = 0, 'fJ2 = 3'fJ1 - - .
3v
(25.24)
A numerical analysis of equations (25.23) and (25.24) was made in [5]; the
result is presented in Fig. 7.9. On the (0", T) plane there exists a point t1 at
which the second-order transition from phase ('fJ, 0) to phase ('fJ1, 'fJ2) changes to
a first-order transition. The point t1 therefore is a tricritical point. The phase
diagram on the (0", T) plane is shown in Fig. 7.10.
''It
(a) (b)
Fig. 7.9. Temperature and pressure dependence of the order parame-

ters for the structural phase transition in A-15 compounds [5] for the
phase ('fJ0) (a) and for the phase ('fJ1'fJ2) (b).
The phase diagram given in Fig. 7.10 (uniaxial stress 0"2 = 0) may be
regarded as the cross-section of a more general phase diagram (Fig. 7.11) cor-
responding to arbitrary stresses 0"1 =1= 0 and 0"2 =1= 0 [6]. The diagram presented
in Fig. 7.11 may be viewed as consisting of three phase diagrams such as those
sketched in Fig. 7.10, which are located at an angle of 1200 relative to each
other. Such diagram symmetry is a consequence of the fact that the initial
(5
0
~'I'tO)
it'
(If,'I'2) .\
T
Fig. 7.10. Phase diagram of a tetragonally deformed A-15 crystal with

uniaxial stress along [001]. The solid line refers to first-order transitions;
the dashed line refers to second-order transitions.
Fig. 7.11. Phase diagram in the case of spontaneous strain in A-15 com-
pounds. q, quadrupolar point; tl, t2, and t3, tricritical points.
phase is cubic and therefore a symmetry with respect to the permutation of

x, y and z should take place.
As a general result of investigating the phase diagram in the case of multi-
component OP's, we may state that phases of equal energy that correspond to
different domains are split up by an external field. Splitting occurs when each
domain is specified by a spontaneous macroscopic quantity that is oriented in
different ways relative to the external field conjugate to this macroscopic quan-
tity. As a function of the magnitude of field, the crystal may be converted to a
one-domain state. This subject is taken up in detail in the last section of this
226 CHAPTER 7
chapter.
SPLITTING OF A PHASE TRANSITION DESCRIBED BY A MICROPARAMETER IN

AN EXTERNAL FIELD
In the preceding section we analyzed the effect of a field conjugate to a macro-

scopic OP on a phase transition. We now consider the case of an indirect
influence of the field on the microscopic OP in terms of the associated macro-
parameter conjugate to the external field. We examine the situation by the ex-
ample of a two-component OP ('f}1, 'f}2) that is related to macroscopic variables
Xl and X2 conjugate to the external fields Xl, X 2 . The potential is chosen in
the form
<1> = r('f}f + 'f}~) + U1'f}f'f}~ + u2('f}f - 'f}~)2 + K 1xf + /(2X~+

+81'f}1'f}2 X 1 + 8 2('f}f - 'f}~)X2 - X1 X 1 - X2 X 2. (25.25)
The phase transition splitting effect can be seen if we pass over to an

effective potential depending only on the parameters 'f}1 and 'f}2. To this end, we
minimize the potential (25.25) with respect to Xl and X2' From the equations
0<1> / OX1 = 0 and 0<1>/ OX2 = 0, we express Xl and X2 in terms of 'f}1, 'f}2 and
Xl, X 2 . On substituting the resulting expressions into equation (25.25), we
arrive at the effective potential
(25.26)
in which we have set Xl = 0 and introduced the notation

X 2 82
r1 = r + 2/(2' r2 = r - X 282(2/(2)-1,
(25.27)
u~ = u1 - 8i(4/(d- 1, u~ = u2 - 8~( 4/(2)-1.
The effective potential contains two quadratic invariants, r1 'f}f and r2'f}~. This
implies that under the effect of the external field X 2 the two-dimensional rel-
evant IR has split up into two one-dimensional representations, as a result of
the lowering of the 'crystal plus field' system's symmetry. Thus we have passed
on to the problem of two coupling OP's (treated in detail in §20). At certain
values of the field X 2, as well as of the other coefficients of the potential (25.26),
a phase diagram with a tetracritical point (Fig. 5.1) may be realized. As a
result, as the temperature is lowered a ('f}1, 0) or (0, 'f}2) type phase should
arise first; it is only when the temperature is decreased further that a ('f}1, 'f}2)
type phase occurs. On the other hand, in the absence of fields, Xl = X2 = 0,

the phases (1]1, 0) and (1]1,1]2), as the different solutions to the equations of
state, border on the initial phase (§17). Thus the indirect effect of an external
field on the OP may lead to splitting of a phase transition into two transitions
whose temperatures are close in magnitude. Phase diagrams for different values
of the field X 2 have been constructed in [7].
It is evident from the arguments adduced above that a phase transition
splitting due to external effects may occur subject to the following conditions.
The IR that describes the transitions should be multidimensional. The trans-
formation properties of the multicomponent OP should be such that the corre-
sponding thermodynamic potential allows the existence of several dissymmetric
phases. The transition to each of these phases should be accompanied by the
occurrence of spontaneous macroscopic properties which are distinct for dif-
ferent phases. These properties should be susceptible to generalized forces
conjugate to them, for example pressure, magnetic field, and electric field.
One more example of phase transition splitting is the structural and mag-
netic phase transitions in KMnF 2 which we have considered in §20. The role
of the external field here is played by the crystal distortion arising from the
structural transition. It is this distortion that leads to the magnetic transition
splitting up into two: At 88.3 K the crystal distortion gives rise to a collinear
anti-ferromagnetic structure with the magnetic moments oriented along the
initial-phase cube edge parallel to the four-fold axis of the distorted crystal; at
the temperature 81.5 K an orientation transition occurs in which the magnetic
moments lie in the basal plane.
26. Features Peculiar to the Temperature Behavior of Susceptibility

in the Vicinity of the Second-Order Phase Transition
CLASSIFICATION OF THE SINGULARITIES BY THE AIZU INDICES
An important step in the study of phase transitions in crystals is the analysis of

anomalies in physical properties in the vicinity of the second-order transition,
in particular of susceptibility anomalies. As has been shown by Aizu [8], some
important conclusions concerning the temperature dependence of generalized
susceptibilities may be drawn from an analysis of a particular type of interplay
of the OP's with macroscopic variables without performing detailed calcula-
tions. To reveal general regularities in the temperature behavior of generalized
susceptibilities, we rewrite the potential (22.1)-(22.5) in simplified symbolic
228 CHAPTER 7
form:
<P = <Po(T) + <PI) + <Px + <Pint, (26.1)
<PI) = r'f/ 2 + P ( 'f/4 ) + P( 'f/ 6) +

·
... , (26.2)
<PX = -/(X - tLX2 - ... , (26.3)
<Pint = -Xg1('f/) - ~Xg2('f/)X - ... , (26.4)
where 'f/ == {'f/1,'f/2, .. .}, X == {X 1,X2, ... } is the contracted notation of the OP
and of the generalized force acting on the system. The starting point in our
analysis is the equation of state for the OP (o<P/O'f/ = 0)
(26.5)
and the expression for the generalized coordinate
(26.6)
obtained from the definition (25.5).

Differentiating equation (25.5) with respect to the generalized force X
gives the expression for the generalized susceptibility
(26.7)
where the symbol s signals the fact that instead of 'f/ we should substitute a
value of 'f/. that satisfies the equation of state. We transform the second term
in equation (26.7) by representing it first as
( d91('f/)) = 2:(091('f/)) (O'f/)..) . (26.8)

dX • ).. O'f/).. • oX •
The relation between the variables 'f/).. and X is given by the equation of state
(26.5), which will be written in the form 1/;('f/, X) = O. From this it follows
immediately that
01/; + 2:(
01/;) (O'f/)..) = O. (26.9)
oX ).. O'f/).. oX
Substitution of the explicit expression for 1/;( 'f/, X) into this equation yields the
epxression for the quantity (O'f/)../ oX).
(26.10)
On solving this equation, we find
(26.11)
which contains the matrix
Inserting equations (26.11) and (26.8) into equation (26.7) gives the final ex-
pression for the generalized susceptibilty x:
(26.12).
This equation tells us that the peculiarities in the temperature dependence of

generalized susceptibilities are determined by the explicit form of the polyno-
mials gl(1]), g2(1]) and by the matrix of the second-order derivatives >.p(1]).
The explicit form of the polynomial gl (1]) depends on the symmetry of
the initial phase and on the form of the generalized forces considered in this
problem. We introduce the index nM, which is equal to the lowest degree of
the OP components involved in the polynomial gl(1]):
(26.13)
When substituting spontaneous values of the parameter 1], part of the terms
involved in the polynomial gl (1].) may cancel out in the case of a multi compo-
nent OP. We introduce the index nF, which is equal to the lowest degree of the
o P components contained in the polynomial gl (1].). Following Aizu, we call
these indices faintness indices. If, by virtue of the symmetry of a particular
problem, the polynomial gl(1]) == 0, then, according to Aizu, we will assume
that nF = 00 and nM = 00.
Since the classification of susceptibilities under consideration relates to
second-order phase transitions, it will be assumed, as usual, that only one
coefficient in the potential (26.1)-(26.4) depends on temperature: r = r~(To -
T). Then, evidently, the following relations hold:
1]. '" ( To - T). 1/2 , (26.14)
(26.15)
230 CHAPTER 7
where the <Pi ('fl.) are the eigenvalues of the matrix 11> AI' ('fl.). Again following
Aizu [9], the indices Pi will be called catastrophe indices. Finally, as shown in
§25, the lowest degree of the 'fli components involved in g2('fl) is equal to two,
so we may set
(26.16)
in the vicinity of the phase transition. We now analyze the temperature depen-
dence of the second term in the generalized susceptibility (26.12). Allowance
for the relations (26.14), (26.15), and (26.7) yields
(d~l'fl)) s ~ (To - TtM-P-l, (26.17)
P being the smallest of the indices Pi in equation (26.15).

First we examine the susceptibility (26.12) in the initial phase near the
transition temperature (T -. To). If nM > I, then the second and third terms
in equation (26.12) in the intial phase ('fls = 0) are equal to zero and the
generalized susceptibility X is temperature independent:
X = L, (nM> 1). (26.18)
In the case of nM = 1 we evidently have the relation

(26.19)
For the indices P = 1 equation (26.19) coincides with the Curie-Weiss law.
We now let T be less than To. The expressions (26.12), (26.16) and (26.17)
then yield
X - L '" (To - T)-l, (nM - P = 0), (26.20)
that is, the Curie-Weiss law holds in the dissymmetric phase. Note that,
according to the relation (26.19), the Curie-Weiss law also holds in the initial
phase if nM = 1. For nM > 1 the susceptibility in the initial phase, according
to the relation (26.17), does not depend on temperature. From the expressions
(26.16) and (26.17), it follows also that
X - L ~ (To - T), (nM - P = 2). (26.21)
Finally, when nM - P 2: 3 the dominant contribution to the susceptibility

comes only from the third term in equation (26.12), namely, g2('fls) , and the
expression (26.21) holds again.
In analyzing the generalized susceptibility (26.12) we may, in all of the

situations enumerated above, restrict our attention to the first terms in the
polynomials gl(1]) and g2(1]). And it is only in the case nM - P = 1 that the
necessity arises of allowing for higher degrees in gl (1]).
It is easy to show (see also §27) that if we confine ourselves to the model
of the fourth degree in 1] and to the first term in gl (1]) and eliminate g2 (1]),
then the susceptibility X at T < To in the case nM - P = 1 is independent of
temperature. Consequently, the temperature behavior of the susceptibility X
in this case is determined by higher-order terms.
CATASTROPHE INDICES
We consider possible values of the catastrophe indices Pi. In the initial phase
(T > To) 'xI'(1].) = </>8,X1' and Pi = 1 for any i in view of the fact that 1]. = 0,
so the temperature singularities of the generalized susceptibility at T -+ To + °
are determined only by the value of the faintness index nM and do not depend
on the catastrophe indices. It can be readily verified that in the dissymmetric
phase T < To near the second-order phase transition point (T -+ To - 0), in
the case when the phase transition is described by a one-dimensional IR, the
catastrophe index is equal to unity: P = 1. Thus catastrophe indices with values
other than unity may occur only for phase transitions with a multicomponent
OP.
As an example, we wish to find the catastrophe indices for a 2-component
OP 1] = {1111]2} whose transformation properties correspond to the potential
;r.
'ol' = r (2
1]1 + 1]22) + U (2
1]1 + 1]22)2 + V11]12( 1]12 - 31722)2 + V21]22( 1]22 - 31]12)2 . (26.22)
The matrix ,XI' for a solution of type 1]1 = 1], 1]2 = °has the form
(26.23)
The parameter 1] is found from the equation of state r + 2U1]2 + 3V11]4 = 0,

whence we obtain the result that in the vicinity of the transition point,
2 r
1] :;:::j - - .
2u
Substitution of this expression into equation (26.23) gives
(26.24)
that is, the catastrophe indices are P1 = 1, P2 = 2.

232 CHAPTER 7
It might be as well to point out that the values for the catastrophe indices
depend on the choice of the variables. Indeed, let the potential have the form
(26.25)
The matrix of second-order derivatives for an ('fJ 0) type solution is diagonal:
(26.26)
and determines the catastrophe indices PI P2 1. = =

We introduce new trigonometric variables 'fJI = 'fJ cos ¢ and 'fJ2 = 'fJ sin ¢ in
which the potential (26.25) becomes
(26.27)
The matrix of second-order derivatives in this case has the form

<1>1/1/ = 2[r + 6UI 'fJ2 + 6U2'fJ 2 cos 4¢],
(26.28)
= <1><1>1/ = -16 u 2'fJ3 sin4¢, <1><1>4> = -16u2'fJ4cos4¢.
<1>1/<1>
The conditions sin 4¢ = 0, cos 4¢ = 1 and 'fJ2 = - 2(til~ti2) correspond to the

solution type ('fJ 0). Substituting these into equation (26.26) gives
(26.29)
that is, the catastrophe indices are PI = 1, P2 = 2. By analyzing different

examples, it can be verified that one of the eigenvalues of the matrix <l>AI'('fJ)
for second-order phase transitions is [-4r2 + 0(r 2)]. Aizu has formulated this
fact as a theorem [10] and proved it for the general form of the potential <1>1/ in
the 'fJ4 model.
An analysis of the point group IR's [11] has shown that the maximal value
of the catastrophe indices for the point groups is equal to two (Pmax = 2). All
one-dimensional IR's have index P = 1. For the two-dimensional IR's of the
trigonal, hexagonal and cubic point groups that satisfy the Landau criterion,
the catastrophe indices are PI = 1 and P2 = 2. The two-dimensional IR's of
the tetragonal groups have the indices PI P2 = =
1. Finally, for the three-
dimensional IR's of the cubic groups that satisfy the Landau condition, all
indices Pi are equal to unity (PI P2 P3 1). = = =
Thus an analysis of the general form of the thermodynamic potential has
shown that anomalies in the temperature dependence of generalized suscepti-
bilities are determined by the type of interaction of the OP with the generalized
forces (or generalized coordinates). The temperature behavior of the suscep-

tibility is determined by the faintness index nM and the minimal catastrophe
index p.
27. Calculation of Susceptibilities for

Second-Order Phase Transitions
PROPER PHASE TRANSITIONS
Measurement of the generalized susceptibility X = (ax/aX) near the phase

transition point is one of the major sources supplying information on the pres-
ence of a transition in a given compound, on the kind of transition, on the
transformation properties of the OP and on the value of the coefficients in the
thermodynamic potential.
We calculate the susceptibility in the vicinity of the second-order phase
transition point. Take the simplest potential
(27.1)
where u > 0. In this representation of the presence of an external field is

taken into account, as stated in §25, by writing out the equation of state
(27.2)
The expression (27.2) immediately yields the inverse susceptibility:
(27.3)
The condition for the dissymmetric phase to be stable, 0 2 /0"1 2 > 0,
reduces to the requirement that the inverse susceptibility be positive:
(27.4)
Substituting the spontaneous parameter "Is (that is, the equilibrium value
of the parameter "I in a zero field) into equation (27.3), it is easy to find the
isothermal inverse susceptibility (T < To):
x- 1 = -41' = -41'h(T - To). (27.5)

234 CHAPTER 7
Above the transition temperature (T > To) we have in the initial phase
(where TJ = 0)
(27.6)
The resulting expressions lead to Landau's 'law of 2' [12] which means that
at the same distance from the transition temperature the susceptibility in the
symmetric phase is twice as large as the counterpart in the dissymmetric phase.
The temperature dependence of the susceptibility X satisfies the Curie-Weiss
law on either side of the transition.
IMPROPER PHASE TRANSITIONS
The models considered in the previous section apply to proper transitions. In

the description of such transitions, one may restrict oneself to one OP. We now
consider some of the most important models of potentials describing systems
with two OP's. One of these parameters plays the role of an OP (we label it
by TJ), the other is a macroscopic quantity x measured experimentally.
Consider the potential [13]
(27.7)
and assume that only the coefficient r = rb (T - To) is temperature dependent.

The equation of state for the variable x has the form
(27.8)
In the absence of a field, the spontaneous values of the parameters TJs and Xs
are described by the expressions
(27.9)
2 r
TJ s = - 2u' (27.10)
whence it follows that the variable Xs depends on temperature in a linear
fashion (Fig. 7.12).
We determine the catastrophe index p, that is, the condition for the dis-
symmetric phase to lose stability in a zero field X:
0 2 If>
- = -41'~(T - To). (27.11)
0172
It follows from the expression (27.11) and the definition of the index p (§26),
that p = 1.
Fig. 7.12. Temperature dependence of the spontaneous generalized

coordinate x. in the case of a second-order phase transition (u > 0)
and for nF = 2.
The inverse susceptibility is easily found from the formula (27.8):
x- 1 = (aX) " (01])

ax • = 21\. + 201]. ax 8' (27.12)
Thus if the transformation properties of the parameters 1] and x are such that
a coupling of type 1] 2 X occurs, then the susceptibility X with respect to the
quantity x in terms of the model (27.7) undergoes a discontinuous change at
the transition point:
x- 1 = 2](, (T> To); X- 1 = 2]( -~,

2u
(T < To) (27.13)
and is independent of temperature in the dissymmetric phase (Fig. 7.13) .
.x
Fig. 7.13. Temperature dependence of the susceptibility for second-

order transitions described by the potential (27.7).
We now introduce the field XT/ conjugate to the parameter 1] and calculate
the susceptibility XT/' The field XT/ is defined by the equation
XT/ = (~<l»
u1] x,T
= 2r1] + 4U1]3 + 201]x, (27.14)
which gives the expression for the inverse susceptibility
(27.15)
236 CHAPTER 7
Above the transition point (T > To), "1. = 0, x. = 0 and the susceptibility
conforms to the Curie-Weiss law
X;;-l = 2r~ (T - To). (27.16)
In the dissymmetric phase (T < To) the Curie-Weiss law works well too, but
the 'law of 2' no longer holds:
2
XIj-1 = 4roI ( To - T ) ( 6 u) .
1 - 8f{ (27.17)
From the results obtained, we thus see that the susceptibility corresponding
to the parameter "1, which is viewed as a primary parameter (§21), diverges at
the phase transition point To, whereas the susceptibility corresponding to the
secondary or improper parameter x remains finite within the framework of the
model (27.7).
An interaction of the type "12X (or "12 X), which contains the potential
(27.7) considered above, arises in those cases where the symmetry of the initial
phase allows a linear invariant x. Such a situation may be encountered, for
example, in cubic crystals when account is taken of the interplay of the strain
(x = ta/3) with the OP "1.
Of all the cases that may be described by the potential (27.7), the case
of translational transitions is the most interesting. As already stated in §24, a
special feature of translational transitions is that the symmetry change at the
phase transition point arises only from a change in the translational symmetry
of the crystal while the point symmetry remains unaltered. As a consequence,
such transitions are not accompanied by the occurrence of new macroscopic
spontaneous variables x, so the temperature anomalies in the macroscopic vari-
ables x, allowed by symmetry in each particular case, as well as the generalized
susceptibilities X are important sources of information in the investigation of
translational transitions.
In the foregoing example it was assumed that the generalized thermo-
dynamic variable x was an independent variable in the representation of the
potential (27.7). This way of representing the potential is convenient in finding
inverse susceptibilities, as can be seen from the above computations. In §25
we noted that in some cases it is more convenient to choose generalized forces
X conjugate to x as independent variables. As will be clear from the example
that follows, such representation of the potential is natural in the calculation
of the susceptibilities X.
We now consider another characteristic potential type:
(27.18)
with u > 0 and v > o. An interplay of the type 7]2 X 2 corresponds to the
indices nM = nF = 00. The catastrophe index, just as in the previous example
(potential (27.7)), is equal to unity.
The formula (26.6) says that in the present case the quantity Xs for the
dissymmetric phase is equal to zero. The susceptibility is given by the expres-
SIon
(27.19)
where g2(7]s) = ,7];. On substituting in equation (27.19) the quantity 7]., which
is determinable from the equation of state, we find the temperature dependence
of the susceptibility X [13]:
u, [(
X = L -2 3v 1 - ,
1 - 3vro(T - To)u -2)+t] . (27.20)
The X(T) function is represented in Fig. 7.14.
"r >0
L ----)-
/ Iy<o
,/ I
I T
Tc '
Fig. 7.14. Generalized susceptibility X(T) in the case of second-order

phase transitions u > O. The dashed line shows the contribution of
higher degrees.
An 7]2 x 2 type coupling exists in all the cases where the linear invariant
x is absent. As in the previous example, the results obtained are particularly
important in the case of translational transitions.
In the foregoing we have considered two models of potentials, (27.7) and
(27.18), which describe improper transitions with a one-component OP 7] and
one parameter x, and also improper transitions with two interaction types,
7] 2 X and 7] 2 X 2 respectively. These two models may be employed to describe
improper ferroelastics. However, as shown in [14], they are inapplicable in the
238 CHAPTER 7
case of improper ferroelectic phase transitions. Indeed, if polarization vector

components are chosen as the OP x, then an interplay of the type 'rJ2 x , which
implies that the quantity x is invariant under the initial phase, is impossible in
para-electrics. An interaction of the type 'rJ2x2 is always possible, but, as has
been shown above, the corresponding equations of state contain no solutions
with Xs # O. According to [14], improper ferroelectric transitions may be
described in a model with a two-component proper OP 'rJ = ('rJl'rJ2) that allows
a 'rJl'rJ2X type interaction, that is, in terms of the potential
iF. _
'!' - r (2
'rJl + 'rJ22) + Ul (4 4) 2 2 LX- 2 + 'Y'rJl'rJ2 X ,
'rJl + 'rJ2 + U2'rJl 'rJ2 + (27.21)
where the quantity X coincides with one of the components of the electric field
E.
In the absence of a field the equation of state allows three solutions:
O. 'rJls = 'rJ2s = 0;
2 _ r.
1. 'rJls = 0, 'rJ28 - - 2Ul ' (27.22)
2. 'rJrs = 'rJ~s = -r( 4Ul + U2)-1.
We can readily see that it is only in phase 2 that a spontaneous quantity may
occur alongside non-zero parameters 'rJls and 'rJ2s:
Xs = 'Y'rJls'rJ2s' (27.23)
As with the model (27.7), the spontaneous variable Xs depends linearly on

temperature.
The temperature anomalies of the susceptibility X = (ax/aX)s at the
o +-+ 2 transition, just as in the (27.7) model, reduce to a susceptibility jump
at the transition point:
X = L (T> To);
(27.24)
X = L + 'Y2(4ul + U2)-1 (T < To).
For T < To the susceptibilities are independent of temperature.
PSEUDOPROPER PHASE TRANSITIONS
Returning to the analysis of different types of interplay between the parameters

'rJ and x, we wish to consider one more example, in which the transformation
properties of both parameters are the same. Consider a potential of the form
(27.25)
The potential (27.25) corresponds to the indices nM = 1 and p = 1. The

quantity Xs in the dissymmetric phase turns out to be proportional to the OP
'f]s:
X.=,'f]s· (27.26)
The susceptibilities X above and below the transition point obey the Curie-
Weiss law:
,2
X= L + - (T> To);
2r
,2 (27.27)
X = L - 4r (T < To).
The phase transitions described in terms of the model (27.25) are said to be
pseudo-improper [1]. As an example, we may quote the ferroelastic transition
mmm --+ 21m which occurs at T = -62°C in (NH 4hS04 [15].
28. Singularities of the Susceptibility in the Vicinity

of the First-Order Phase Transition
CLASSIFICATION OF THE FIRST-ORDER TRANSITIONS
As already stated in §16, as a simple model of the potential describing first-
order phase transitions we may take a potential of the form
(28.1 )
where u < 0 and v > O. The equation of state allows two solutions (see
equations (16.5) and (16.6)):
17I = - 3vu [1 - ( 3vr) 1/2]

1- ~ , (28.2)
2 U[ ( 3Vr)1/2]
'f]2 = - 3v 1+ 1- U2 . (28.3)
In §16 the first solution was shown to be an analytic continuation of the unique
solution in the 'f]4 (v = 0) model and to describe a second-order transition. The
second solution (28.3) is absent in the 174 model and occurs for the first time
in the 'f]6 model. This solution describes a first-order transition. Evidently, as
invariants of higher degrees are added the solutions to the equation of state will
increase in number and part of the solutions will be an analytic continuation
of the preceding models, but there will also be 'novel' solutions. It stands to
reason that all the solutions can be classified according to types, laying at the
240 CHAPTER 7
foundation of the classification the sequence in which these occur as higher-

order invariants are added to the potential. This program dates back to Aizu
[16], who introduced the concept of first-order transitions (§16). In keeping
with Aizu's definition, as shown in §16, the solution (28.2) describes a 1 - s
type transition (second-order transition), while the solution (28.3) describes a
2 - s type transition (first-order transition). To derive a 3 - s type solution,
one now has to proceed to the 1]8 model.
To work out practical recommendations as to how first-order transitions
should be identified experimentally, we need to consider singularities in the
temperature behavior of susceptibilities for different transition types.
CLASSIFYING THE SINGULARITIES OF SUSCEPTIBILITIES
To take into account the possibility of first-order transitions of two different

types, we consider a potential that allows for the terms 1]8 [16]:
(28.4)
The equation of state then reduces to the cubic equation
y3 _ 3py - 2q = 0, (28.5)
where
(28.6)
The equation (28.5) has three solutions if p3 - q2 > 0. These may be written
as
v v ( 8uw) 1/2 1
1]
2
sn
= -4w
- - -4w 1- - -
3v 2
cos -(a + 2mr),
3
(28.7)
where n = 0,1,2 and -7r < a < 7r [16]. We have
sin a = 4uw (1 _ 8UW) -3/2 (1 _ 3rv _ 32uw + 12rw _ 12r2w2) 1/2, (28.8)
v'3v2 3v 2 u2 9v 2 uv u 2v 2
8uw) -3/2 ( 4uw 8rw 2 )

cos a = (1 - --
3v 2
1 - -- + -- .
v2 v2
(28.9)
Exploiting the definition of the transition type (§16), we find that the solution
with n = 1 is a 1 - s type solution and describes a second-order transition; the
solution with n = 2 is a 2 - s type solution, while the solution with n = 3 is
of the 3 - s type. The susceptibility XO in the initial phase for 2 - sand 3 - s

transitions is given by
(28.10)
with r = r~ (T-To). The first-order phase transition point is determined from

the condition = o. At T = Tc the solutions 1];,0,2 take on the values
2 V [1- ( 1- -
= -3w
- 3UW) 1/2] , (28.11)
1] 2
s, v 2-
2
= --
1] 0
V [1 + ( 1- -3uw) 1/2] . (28.12)
" 3w v2
Substitution of equation (28.11) or (28.12) into the equation = 0 yields the
value of r at the point T = Tc:
__ 2v 3 [ _ 9uw ( _ 3UW)3/2]
rc - 27 w 2 1 2v 2 =f 1 v2 •
(28.13)
On substituting equation (28.13) into equation (28.10), we find the inverse

susceptibility:
-1 _ _
XO -
4v 3 [ _ 9uw
27w 2 1 2v 2 =f
(1- 3UW)3/2]
v 2 •
(28.14)
We calculate the susceptibility Xd in the dissymmetric phase. To this end,

write out the expression for the second-order derivative of and substitute
into it the expressions (28.11) and (28.12) for 1];,0,2. The result for Xd"I, and
also the expression (28.14) for Xol may be represented as
-1 8v3{){
= 9w )2 , (28.15)
Xd 2 ±R 1 =f R
-1 2v 3 2
Xo = 27w 2 (I ± 2R){1 =f R) , (28.16)
where R = (1- ~) 1/2 [16].

The susceptibility jump at the transition point is
Xo = 12R{2R ± 1)-1 (28.17)

Xd
We now determine the values of the parameters u, v, w at which a 2 - s

type transition will occur and those at which a 3 - s transition will occur.
242 CHAPTER 7
We begin with the 2 - s type transition. The expression for R leads to the
inequality
(28.18)
and the phase stability condition
(28.19)
On the = 0 transition line the inequality for 2 - sand 3 - s type transitions
takes the form
32v 3 R(l _ R) > 0 (28.20)
9w 2 -
- !::R(l + R)2 ~ O. (28.21 )
From the requirement that 1J;,2 > 0 at T = Tc and from the conditions (28.18)-
(28.21), it then follows that a 2 - s type transition is possible when u < 0 and
v > O. For a 3 - s type transition the region of existence is bounded by the
inequality (28.18) and v < O.
We consider in more detail the case v < o. The temperature of a phase
transition of 1- s type (second-order transition) is determined by the condition
'r = o. The 3-s transition temperature is described by theequation (28.13), in
which the plus sign should be retained. From this, it follows immediately that
if the bracketed expression in equation (28.13) is greater than zero at v < 0,
then the temperature Tc for a 3 - s transition is higher than the temperature
To for a 1 - s transition and vice versa. As a result, we may write down the
following constraints on the coefficients u, v, and w for 1 - s, 2 - s, and 3 - s
type transitions:
1- s. v> 0, u> 0 and v < 0, u > v 2(4w)-lj
(28.22)
2-s. v>O, u<Oj 3-s. v<O, u<v2(4w)-1.
It follows from these inequalities that the value of R for 2 - s type transitions
should lie within the limits 1 < R < 00 and for 3 - s transitions, within the
limits ~ < R < 00. By virtue of equation (28.17) we may then write down the
range of variation of the ratio XO/Xd:
2 - s. 4 < Xo < 6, (28.23)

Xd
3 - s. 6 < Xo < 00. (28.24)
Xd
Fig. 7.15. Temperature dependence of the susceptibility near the first-

order phase transition point (u < 0) in the absence of an 1] 2 X type
coupling.
Thus we have obtained a very simple criterion which permits the type of a
first-order transition to be determined from susceptibility measurements. The
results thus obtained refer to susceptibility in terms of proper parameters 1].
CALCULATING THE SUSCEPTIBILITIES
We conclude by finding the form of the temperature dependence of susceptibili-

ties with respect to secondary (improper) variables x for two types of interplay,
1]2 x and 1]2 x 2 • Since we are examining the case of first-order transitions, we
proceed from the potential
(28.25)
setting u < O.
The expression for the susceptibility X = - ({)2~ f {)X 2 ). has the form
(28.26)
where 1]; is described by the formula (28.3).

As can be seen from §16, a non-zero spontaneous OP 1]; (T = Tm) = - 3~
arises at Tm = To+ 3u2 , which corresponds to the metastable phase down to the
vro
=
temperature Tc To + 3uvro \ . At the point T =
Tc a first-order phase transition
comes about. The OP jump at the transition is equal to 1]. (T = Tc) = - ;~.
We see from these arguments that at the transition point Tc the susceptibility
X (28.26) undergoes a discontinuous change: ~X = ,2
flul (Fig. 7.15). The
temperature dependence X(T) is determined by the expressions (28.26) and
(28.3) and is presented in Fig. 7.15.
244 CHAPTER 7
The second interaction type leads to a potential of the form
(28.27)
where, as before, we set u < O. The susceptibility in this model is described by

the expression
(28.28)
As for the temperature dependence of X, it is determined by the function 7];(T),

which has the form of equation (28.3). Shown in Fig. 7.16 is a X versus T plot
for positive and negative values of r.
x (a) x (b)
L-~ I I T
L
Fig. 7.16. Susceptibility anomaly at the first-order transition point in

the case of an 7] 2 X 2 type coupling at r > 0 (a) and r < 0 (b).
29. Domains in an External Field
A THERMODYNAMIC DESCRIPTION OF THE DOMAINS

In the foregoing, when analyzing the low-symmetry phases, no consideration
was given to the domain structure of these phases. However, as already stated
in §23, experimental exploration of the crystal's domain structure and the effect
of an external field on the domain structure provides valuable information on
the phase transitions that occur in crystals. Of the various aspects involved in
the theoretical description of the crystal domain structure, we wish to treat the
behavior of domains in an external field in terms of phenomenological phase
transition theory.
As an example, we probe the hypothetical transition, described in §10, in
ammonium sulphate (NH 4hS04 from the hypothetical paraphase D~h to the
phase D~~ [17,18]. To construct the potential 4>, we need to find the IR that
is responsible for the D1h -+ D~~ transition.
Using the standard techniques outlined in §8, it is easy to find that the IR
sought is the one-dimensional representation T4 of the star of the wave-vector
~1 = ~b1 (star {~12}). Since the star {~12} has three arms, the Dth --+ D~~
transition is described by a three-component OP (171,172,173). The transforma-
tion properties of the OP are described by the three-dimensional matrices of
the representation D induced from the representation T4. By constructing the
matrices of the representation D it can be readily verified that a set of different
matrices of this representation generates an I group isomorphic to the point
group O. Therefore, the potential may be immediately written out in the form
n.
~11 = r (2
171 + 1722 + 1732) + Ul (4
171 + 1724 + 1734) + U2 ( 171172
2 2 2 2 + 172173
+ 171173 2 2) . (29.1)
The 0 P (171, 172, 173) refers to a transition with", i 0, so it does not describe
the macroscopic properties of the dissymmetric phase. To analyze the influence
of an external field on domains, macroscopic variables should be included in the
potential. We choose as these variables the strain tensor components Xi. For
hexagonal crystals the strain-induced contribution is described by a potential
of the form
!fix = ~Cll(xi + xD + ~C33X~ + !C66X~ + C12X1X2 + C 13 (X1 + X2)X3, (29.2)

Cij H
being elastic moduli and C66 = C ll - C 12 ) [19].
To determine the type of interaction of the OP 17>. with the parameters
Xi, we find the constitution of the symmetrized square of the representation D
according to which the OP components transform:
(29.3)
The combination transforming according to the representation T1(A 1g ) is L>.17~

and the basis functions of the representation Tll(E 2g ) have the form 17f +
17~ - 2175 and v'3( 17f - 17~)' To find the symmetrized combinations constituted
by the strain tensor components Xi, we determine the basis functions of the
symmetrized square of the vector representation V:
(29.4)
The symmetrized combinations of the representations T1, T9, and Tll are
T1(A 1g ) :
T9(E1g) : (29.5)
Tll(E2g ) :
246 CHAPTER 7
respectively.
The data obtained enable us to write the form of the coupling type for the
parameters Xi and TJ>.:
<Pint = 8l (Xl + x2)(TJf + TJ~ + TJ5) + 82x 3(TJf + TJ~ + TJ5)+

+83 [(Xl - X2)(TJf + TJ~ - 2TJ5) + V3 X6(TJf - TJ~)]. (29.6)
Prior to exploring the equations of state, we determine the number of

domains and the solution types that correspond to each domain. As shown in
§9, the number of domains is determined by the ratio of the index of the initial
group Dth to the index of the dissymmetric-phase group D~~ and is equal to
six. These six domains may be broken up into three pairs according to different
origins of the two-fold axes in the basal plane. Each pair comprises a domain
of specified orientation and a translational (antiphase) domain with respect to
it, as shown in Fig. 7.17.
bll\)Domlli'>l ~/
e" /
/
a" . /
------~ e,D
a' b'
Doma.i?l I
{J
e"' \
ail' \\
Doma.';. J \
b'" \
Fig. 7.17. Relative position of rotational domains (the number of

rotational domains coincides with the number of arm domains) in
(NH 4hS04 [17,18].
To determine what form the solutions to the equations of state should have
for the different domains, we use the condition for the density function 8p to be
invariant under the symmetry group of the low-symmetry phase. Using three
crystallographic ally equivalent directions, we choose the subgroups D~~ of the
group Dth. This corresponds to three pairs of domains (Fig. 7.17). From the
condition gop = op, where g E D~~, we obtain the equation of state for the OP
components, which gives the form of the solutions for the different domains:
1. 1]1 = ±1], 1]2 = 1]3 = 0;

2. 1]1 = 0, 1]2 = ±1], 1]3 = 0; (29.7)
3. 1]1 = 1]2 = 0, 1]3 = ±1].
The plus or minus sign refers to the pair: domain - translational domain.
In the following we restrict ourselves to an exploration of the solutions
(29.7). On substituting the relations (29.7) into the equations of state fJif> / fJ1]).. =
o and fJif>/fJxi = 0, we find the expressions for the spontaneous OP 1]).. and
strains Xi for each of the domains, 1 to 3, [17,18].
1.
(29.8)
2.
(29.9)
3. xt = ~(C1 - 2C2)1]2, X~' = HC 1 + 2C2)1]2 , (29.10)

X~' = C31]2 , X~' = 0,
where the coefficients C 1 , C2 , C3 and the parameter 1]2 have the form
03
C 1 = 2(02 C13 - 01 C33) [ (C11 + C12 )C33 - 2
2C13 }
-1
,C2 = - C 66 '
(29.11)
C3 = [201C13 - 02(C11 + C12)] [(C 11 + C12 )C33 - 2Cf3r1,
(29.12)
EFFECT OF AN EXTERNAL FIELD ON DOMAINS
The expressions (29.8)-(29.10) tell us that the domains differ in spontaneous

strains. It is this difference that accounts for the fact that the external field
exerts different influences on the domains. For the external field to be allowed
248 CHAPTER 7
for explicitly, we need to add to the potential (29.1), (29.2), (29.6) a term ~int
of the form
~int =~:nt + ~:~t + ~:~t =

= -Xl(X~ + xr + xr') - X2(X~ + x~ + x~')
-X3(X~ + x~ + x~') - X6(X~ + x~ + x~'), (29.13)
which describes the interaction energy of all the three domains with the exter-
nal fields Xi (in the present example Xi stands for the external-stress tensor
components).
Consider the case of uniaxial pressure: Xl < 0, X 2 = X3 = X6 = O. From
the expressions (29.8)-(29.10) and (29.13) it follows that ~:~t < ~:~t = ~int.
In the case of uniaxial pressure the domain boundaries in the crystal should
therefore be expected to shift in such a way that the domains 1 and 2 vanish
and, as a result, a single-domain state may be reached (the coefficient C 2 is
assumed to be positive [17,18].
By applying uniaxial pressure along the other axis in the basal plane of
the initial phase D~h X 2 < 0, Xl = X3 = X6 = 0, we get ~i~t > ~i~t = ~int'
that is, the domain to vanish in this case is the domain 3, and the domains 1
and 2 should occupy equal volumes of the sample.
The results of experimental investigations into the effect of pressure on
the domain structure in (NH 4hS04 are in good agreement with the picture
described above. This provides further conclusive evidence that the paraphase
D~h has been chosen correctly in these compounds (§10).
From the example considered, it is clear what one should expect in the
general case. It is evident that application of an external field should lead
to shifting of the domain boundaries and to conversion of the sample to a
single-domain state in all the cases when the change of the point symmetry
of the crystal allows the occurrence of spontaneous macroscopic properties:
strain, polarization, magnetization [19,20]. Owing to the difference of these
quantities in different domains, directional influence may then be exerted on
the domain structure by applying to the sample an external field conjugate to
these quantities: pressure, electric field, magnetic field. What has been said
above holds good also for higher-order ferroics, when the low-symmetry phase is
characterized by the occurrence of macroscopic properties that are described by
high-rank tensors (§23). For the domain structure to be affected, the sample in
this case should be subject to certain combinations of external fields of different
nature: pressure and electric field, pressure and magnetic field, etc.
References
1. M.E. Lines, and A.M. Glass: Principles and Application of Ferroelectrics

and Real Materials, Clarendon Press (1977).
2. R. Eline, and B. Zeks: Soft Modes in Ferroelectrics and Antifer1'Oelectrics,
Elsevier-North Holland (1974).
3. A.B. Western, A.G. Baker, C.R. Bucon, and V.H. Schmidt: Phys. Rev. B
17,4461 (1978).
4. S.V. Vonsovsky, Yu.A. Izyumov, and E.Z Kurmaev: Superconductivity of
Transition M etals, their Alloys and Compounds, Springer Series in Solid-
State Sciences 27, Springer-Verlag (1982).
5. B. Pietrass: Phys. Status Solidi (b) 68, 553 (1975).
6. N. Srabo: J. Phys. C 8, L397 (1975).
15. J. Kobayashi, Y. Enomoto, and Y. Sato: Phys. Status Solidi (B) 50, 335
(1972).
16. K. Aizu: Phys. Rev. B 23, 1292 (1981).
17. Y. Makita, A. Sawada, and Y. Takagi: J. Phys. Soc. Japan 41,167 (1976).
18. Y. Sawada, Y. Makita, and Y. Takagi: J. Phys. Soc. Japan 41,174 (1976).
19. Yu.I. Sirotin, and M.P. Shaskol'skaya: Osnovy Kristallofisiki (Fundamen-
20. G.A. Smolenskii, V.A. Bokov, V.A. Isupov et al.: Segneto-elektriki i anti-
segnetoelektriki (Ferroelectrics and an tiferroelectrics) , Nauka
(1971).
CHAPTER 8
Martensite Transformations
30. Reconstructive Structural Transitions
TRANSITIONS WITHOUT GROUP-SUBGROUP RELATION
The previous chapters dealt with first- and second-order transitions at which
the symmetry group G 2 of the low-symmetry phase is a subgroup of the parent-
phase symmetry group G 1 : G 2 C G 1 . Such transitions are called group-
subgroup related transitions. In addition to these, there exist also so-called
reconstructive phase transitions, at which the condition G 2 C G 1 is not fulfilled,
that is, the low-temperature-phase symmetry group G 2 is not a subgroup of
the high-temperature-phase symmetry group G 1 .
Two reconstructive phase transition types are distinguished [1]. One of
them includes transitions due to diffusion processes. Transitions of the second
type include those realized by cooperative displacement of crystal atoms. In
the following we concentrate on the second type of transitions.
The consistent diffusionless character of displacements at reconstructive
phase transitions of the second type provides a basis for constructing a variety
of schemes that describe the crystallographic relation of the phases G 1 and G 2
[2,3]. Two cases may evidently be singled out. In the first case the groups G 1
and G 2 are subgroups of one common supergroup Go : G 1 eGo, G 2 eGo,
and G 1 and G 2 are not group-subgroup related. Then, choosing the phase G 2
as the parent phase, standard Landau theory methods (see Chap. 5) enable
one to construct a phase diagram. The relative position of the phases on the
phase diagram is sketched in Fig. 8.1. It is seen that a chain of transitions
Go ~ G 1 ~ G2 is possible under certain conditions (thermodynamic path
A - B). The last link in this chain is a reconstructive transition G 1 ~ G 2 .
Such a situation occurs in many crystals that undergo a series of struc-
tural phase transitions. For example, the cubic perovskite BaTi0 3 exhibits
250
MARTENSITE TRANSFORMATIONS 251
Fig. S.l. Phase diagram for group-subgroup related transitions: Go -+

G 1 , Go -+ G 2 . A-B thermodynamic path including the phase change
G1 -+ G2 .
at T = -SO°C a phase transition from the orthorhombic phase G l =C~; to

the rhombohedral phase G 2 = cgv ' Alongside these two phases, a cubic high-
temperature phase Go = Ok is realized in BaTi0 3 . Choosing this phase as the
parent phase, we can readily verify by the Birman criterion (§S) that the tran-
sitions Go -+ G l and Go -+ G 2 are described by the same three-dimensional
IR 710 of the group Ok point r, but by different mixing coefficient types (dif-
ferent types of solution to thermodynamic potential minimization equations):
710(C C 0) for G 1 and 710(C C C) for G 2 . Consequently,the G l -+ G 2 tran-
sition may be described by a single three-component OP. In the general case
the phases G 1 and G 2 are not necessarily described by the same IR of the
parent-phase symmetry group Go. Thus two tetragonal phases G l and G 2 in
Nax W0 3 correspond to two different IR's, one of which belongs to the point
X and the other to the Brillouin zone point M of the high-temperature cubic
phase Go = Ok.
Another class ofreconstructive transitions is represented by transitions be-
tween the phases G l and G2, the symmetry groups of which are not subgroups
of one common supergroup Go. Examples of such transitions are polymor-
phous transformations [1]. Thus, at low temperatures, iron is in the a-phase
with b.c.c. structure. At Tl = 910°C a reconstructive transition to the ,-
phase with f.c.c. structure takes place. Finally, at T2 = 1400°C the ,-phase
is succeeded by a 8-phase with b.c.c. structure. At elevated temperatures,
an h.c.p.-b.c.c. transition takes place in zirconium, titanium, thallium, and
lithium. A reconstructive transition from h.c.p. phase to f.c.c. phase during
heating occurs in calcium, lanthanum, and scandium. In this case the sym-
metry analysis of the crystallographic relation of two phases reduces to an
exploration of their common subgroup [2,3]: G s = G l n G 2 , G s C G l , and
252 CHAPTER 8
Gs C G2 ·
By convention, the phase transition G 1 -+ G 2 may be broken up into two
stages by introducing a hypothetical intermediate phase G. : G 1 -+ G s -+ G 2 •
In a number of cases such an intermediate phase has been detected experimen-
tally. For example, CU2Te exhibits a reconstructive phase transition D~h -+
O~. Using various experimental techniques [4], several intermediate phases are
recorded over the temperature interval between 30 and 40°C. A similar picture
is observed in Cu 2S, ZnS, and GdS [5].
Reconstructive transitions via an intermediate phase embrace transitions
in interstitial solid solutions [6,7]. As a function of interstitial atom size and
concentration, either ordering-type transitions giving rise to a superstructure
(see §4) or reconstructive transitions may occur in interstitial solid solutions.
Superstructures occur predominantly in transition metal hydrides since hydro-
gen weakly distorts the metallic lattice, whereas nitrides and carbides display
chiefly reconstructive transitions. For example, with interstitial solid solutions
of carbon in b.c.c. metals of composition Me2X (Me=V, Nb, Mo, W; X=C) a
reconstructive transition gives rise to a structure with an h.c.p. lattice [6].
Group-subgroup related structural phase transitions, as a rule, satisfy Lan-
dau's concept of the transition going over one IR, that is, the concept that the
restructuring of the crystal structure at such transitions is described by modes
of one of the parent-phase symmetry group IR's. At reconstructive phase tran-
sitions the crystal lattice restructuring cannot be described by modes of a single
IR. A feature peculiar to reconstructive transitions is that along with displace-
ment modes, lattice deformation plays an important role in the restructuring
of the crystal structure. Thus shear deformation of (110) planes along [110] [8]
directions plays a leading role in the b.c.c. - f.c.c. transition.
Phase transitions in which deformation plays a determining role show typi-
cal anomalies in physical properties, a fact which provides grounds for isolating
such transitions into an individual class, the class of martensitic transitions [9].
Characteristic features of martensitic phase transitions are [1]: (1) the phase
transformation is realized when the temperature is varied, (2) the martensitic
transitions are accompanied by a substantial change in sample shape, (3) the
formation of a new phase proceeds at a high rate, and (4) deforming the sample
promotes a martensitic transition.
It should be emphasized that both reconstructive transitions, for example
the a - 'Y transformation in iron, and continuous transitions, for example the
structural phase transition O~ -+ D~h in A-15 compounds, may belong to
martensitic transitions. In the following we give predominant treatment to

reconstructive martensitic transformations.
GEOMETRIC RELATION OF DIRECT LATTICES
To establish a geometric relation between the transformation products, a know-

ledge is required of either the path that the atoms travel at the transition or
the displacement modes that participate in this path. Searching for the path
traversed by atoms at a reconstructive transition is not a constructive procedure
since for the same transformation in different crystals, the path will be different.
Indeed, since several more displacement modes, called reshuffles, participate in
the martensitic phase transition, in addition to deformation, the path of each
atom from the initial to the final position will be determined by the ratio of
these constituents. Therefore, in discussing martensitic transformations, the
most informative way is by finding these modes.
The geometric relation of lattices at martensitic phase transitions may be
established by analyzing the relative position of the initial- and final-phase re-
ciprocallattices [2] or from parent-phase crystal structure models, the simplest
of which is the solid-spheres model [10-12].
Henceforth we call the high-temperature phase an austenite, and the low-
temperature a martensite. As the austenitic phase we take the h.c.c. structure
and assume that this structure is formed by atoms of radius R. Figure 8.2
presents two sections of such a lattice, along the edge and along the face diag-
onal. It is easy to see that displacement of one of the atoms of such a crystal
in any direction, except the [110] direction, leads to displacement of all the
atoms of the crystal. Only displacement along the face diagonal ([110]-type
direction) should lead to displacement of part of the atoms, namely those lying
in the (110) plane. Thus displacements along face diagonals are the most favor-
able; it is these displacements that are assigned a leading part in martensitic
h.c.c.-h.c.p. and b.c.c.-f.c.c. transformations [13].
Let us isolate, in a crystal with b.c.c. structure, the (110)-type planes
and number the atoms as shown in Fig. 8.3. Consider the displacements of
these planes relative to each other. To this end, it is convenient to regard
one of the planes (in Fig. 8.3 this is the plane Po) as fixed. Depending on
displacements of the adjacent planes relative to the reference plane, two cases
may be distinguished, as depicted in Fig. 8.4. In the first case (type A) the
planes lying to the right and left of the reference plane are shifted in opposite
directions. In the second case (type B) the planes lying to the right and left
254 CHAPTER 8
(a) (b)
Fig. 8.2. Projection of the b.c.c. structure on the (001) plane (a) and
on the (110) plane (b).
of the reference plane are displaced in one direction by the same amount. In
both cases the adjacent planes are shifted relative to each other by the same
amount ~.
Q
II
L, •'6
0
,2) i
-
1/ ]~----
'7 16 --1/
/!J" ./ c / fI' r> !J
9
.,/'
,.:'5
X
0
3 "1/
,
_C
'
II
2
Fig. 8.3, b.c.c. structure. Po and P± stand for (llO)-type planes.

Fig. 8.4. Major atomic displacement types participating in martensite

tr ansformations.
THE b.c.c.-f.c.c. TRANSITION
Let us see what kind of structure results from the realization of type A dis-
placements in the b.c.c. structure. For this type of displacement we assume the
Po plane (Fig. 8.3) to be fixed. We denote the displacements of the atoms lying
in the P+ plane by solid arrows (Fig. 8.5) and those of the atoms lying in the
P _ plane by dashed lines. The numbering of the atoms presented in Fig. 8.5
coincides with that of the atoms of the b.c.c. structure sketched in Fig. 8.3. As
a result, a three-layer structure such as that shown in Fig. 8.6 arises which, by
the type of layer arrangement, is reminiscent of an f.c.c. structure. The result-
ing three-layer structure differs from the h.c.p. structure in that the triangles
isolated in Fig. 8.5 are not equilateral. We can satisfy ourselves that for an
h.c.p. structure to be obtained, it suffices to compress the resulting three-layer
structure along the z axis and to extend it along the [110] directions. These
additional atomic shifts are shown in Fig. 8.5 by dotted lines.
The magnitude and direction of extra shifts at the b.c.c.-f.c.c. transition
may be obtained using the solid spheres model [11]. One of the conditions
that the solid spheres model satisfies is the requirement that the number of
abutment joints of spheres be maximal for a given type of packing. When the
atoms of one of the (110)-type planes are displaced along [110] by scheme A this
256 CHAPTER 8
Fig. 8.5. Projection of the b.c.c. structure on the (110) plane. The
solid arrows show displacements of atoms lying in the P+ plane; the
dashed arrows show displacements in the P _ plane; the dotted lines
represent extra displacements. The numbering of the atoms is the
same as that in Fig. 8.4. 0, atoms of the P+ plane; *, atoms of the
P _ plane; 0, atoms of the Po plane.
Fig. 8.6. f.c.c. structure and its projection on the (111) plane. 0,
atoms of the Po plane; 0, atoms of the P+ plane; *, atoms of the P_
plane.
condition is violated. It is by restoring the maximal number of abutment joints

in the new structure that we obtain additional displacements. The relative
orientation of the b.c.c. and f.c.c. structures is shown in Fig. 8.7 [14].
THE b.c.c. - h.c.p. TRANSITION

Similarly, displacements of atoms of a b.c.c. structure by scheme B may be
shown to lead to an h.c.p. structure. Inspection of Fig. 8.8, which presents
~.-
/
/
/
o
•
/
/
I /
/
/.;:;-
~"'//
/
/
/ '-; / """/o-::---+--:::---tl·-"---:M
1/ /
Fig. 8.7. b.c.c. - f.c.c. transformation.
Po and P± planes and type B atomic displacements, shows that a two-layer

packing results which is typical of h.c.p. structures (Fig. 8.9). Just as in the
previous case of b.c.c. - f.c.c. transformations, additional axial compression
and additional extension along the [110] direction are needed for the structure
resulting from the realization of type B displacements to become an h.c.p.
structure. As for the b.c.c. - f.c.c. transitions, the magnitude and direction of
additional displacements may be obtained in the solid-spheres model.
THE f.c.c. - h.c.p. TRANSITION
In addition to the displacement types A and B describing b.c.c. - f.c.c. and

h.c.c. - h.c.p. transitions, one more atomic displacement type (type C), de-
scribing an f.c.c. - h.c.p. transition, is considered in the literature [15]. Dis-
placements of this type are sketched in Fig. 8.lD. Type C displacements ensure
the reconstruction of the three-layer f.c.c. structure into a two-layer h.c.p.
structure, as depicted in Fig. 8.11. The relative orientation of the f.c.c. and
h.c.p. structures is shown in Fig. 8.12 [14].
Diagrammatically, Fig. 8.13 presents the relation of the most common
b.c.c., f.c.c. and h.c.p. structures and shows the role of A-, B-, and C-type
displacements in transformations among these [15]. The b.c.c. ~ h.c.p. transi-
tion is realized in pure iron. When cooled, thermoelastic alloys Cu-AI-Ni suffer
a b.c.c. ~ h.c.p. transition [8]. By applying stress, the h.c.p. phase (2H)
may be converted to a rhombohedral modification and, on reaching certain
values of applied stress, to an f.c.c. phase (ajJ This situation is portrayed at
the bottom of the diagram in Fig. 8.13. The upper portion of the diagram,
258 CHAPTER 8
showing an intermediate six-layer structure, is realized, for example, in Fe-Mn-

C alloys [16].
Fig. 8.8. Projection of the b.c.c. structure on the (110) plane. The
solid arrows show displacements of atoms in the P+ and P_ planes;
the dotted lines represent extra displacements. The numbering of the
atoms is the same as that in Fig. 8.4; the symbols are the same as
those used in Fig. 8.5.
&4
@-
Fig. 8.9. h.c.p. structure and its projection on the (001) plane .• and
0, atoms lying in the planes z = 0 and z = ~ respectively.
ORIENTATION RELATIONS
A feature typical for orientations of b.c.c., f.c.c and h.c.p. lattices relative to
one another at reconstructive transitions is the presence of invariant planes
and parallel crystallographic directions of these lattices. It is this fact that
provides a basis for introducing the concept of orientation relations. Namely,
Fig. 8.10. Schematic representation of C-type displacements.
Fig. 8.11. Projection of the f.c.c. and h.c.p. structures. The symbols
are the same as those used in Figs. 8.6 and 8.9. The arrows indicate
C-type displacements of the atoms.
:2 3
P;---i\
1\'1/ \
4 I - - \~I
Q,- "
0 - - -I" 6
olvIs' J1",
\ \ I
\/.--v
(a) (b)
Fig. 8.12. f.c.c. - h.c.p. transformations (a) and projections on

the (l11)/.c.c. plane (b). The dashed line outlines the h.c.p. unit
cell. The double arrows show atomic displacements at f.c.c. - h.c.p.
transformations.
an orientation relation implies specification of invariant planes and parallel

directions of austenitic and martensitic phases. As is seen from Figs. 8.5 and
260 CHAPTER 8
Fig. 8.13. Role of A-, B-, and C-type displacements in transformations

among b.c.c., f.c.c., and h.c.p. structures.
8.6, the orientation relations for the b.c.c. - f.c.c. transition have the form [17]
(l10h.c.c. II (111),.c.c.; [111h.c.c. II [llO],.c.c. (30.1)
Similarly, we can determine from Figs. 8.8 and 8.12 the orientation relations
for b.c.c. - h.c.p. transformations:
(l10h.c.c. II (OOOl)h.c.p.; [111h.c.c. II [1000h.c.p. (30.2)
and for f.c.c. - h.c.p. transformations:
(l11),.c.c. II (OOOlh.c.p.; [IIO],.c.c. II [1000]h.c.p .. (30.3)
The lattice restructuring versions considered in the beginning of this sec-

tion are based on simple geometric considerations: minimal distances by which
the atoms are shifted and the geometry of the model of rigid ionic radii (solid
spheres). The orientation relations (30.1)-(30.3) are a mathematical represen-
tation of this geometric relation of lattices. It is these relations that are the
subject of intensive experimental investigations aimed at verifying the geomet-
ric picture drawn. However, these relations are only approximately fulfilled in
experiment. This indicates the impossibility of a coherent reconstruction of
the lattice in the entire volume by the schemes that have been proposed. The
latter are an idealization of the reconstructive transitions. In reality a transi-
tion by the above schemes may occur only in local regions of the crystal. Thus
the problem arises of joining these coherent areas and it becomes necessary to
introduce inhomogeneous states at martensitic transitions.
INTERRELATIONSHIP OF RECIPROCAL LATTICES
One of the major methods of deriving information about martensitic trans-

formations is X-radiography. The data obtained furnish information on the
interrelation between the reciprocal lattices of the high-temperature and low-
temperature phases. Analysis of this interrelationship permits one to extract
information about the atomic displacements that lead to a given transforma-
tion.
Assume that at temperature T1 a phase transition occurs that is accompa-
nied by atomic displacements. As a result, the symmetry of the crystal lowers
and is described by one of the subgroups G s of the parent-phase symmetry
group G 1 . The reciprocal lattice either is distorted, if the wave-vector ", of
the corresponding displacement mode is equal to zero, or new sites arise in the
reciprocal lattice in the case of", =F O. In the diffraction picture the distortion
of the reciprocal lattice manifests itself in the splitting of degenerate reflections
(Fig. 8.14a), and the appearance of new sites corresponds to the formation of
superstructural reflections (Fig. 8.14b). On reaching critical magnitudes of dis-
placement, the symmetry of the crystal heightens to the group G 2 (G s C G 2 ).
In this case the diffraction pattern should display a reverse process; that is to
say, part of the reflections should become degenerate (Fig. 8.14a) or extinct
(8.14b).
As a particular example, we examine the b.c.c. - h.c.p. transition in the
substitutional solid solutions V 2C, Nb 2C, M0 2 C, W 2C, and NbN 0.95 [2]. The
interstitial C and N atoms are located on the octahedral interstitial sites of the
metallic b.c.c. lattice. Suppose that an MeX-type tetragonal superstructure
(see §4) such as that shown in Fig. 8.15 forms owing to the ordering of inter-
stitial atoms. The wave-vector of the structure is "'1 = (~~O). The ordering
of interstitial atoms results in displacement of the metallic atoms indicated by
arrows in Fig. 8.15. Also shown in Fig. 8.15 is the relative position of the
unit cells of the ordered and disordered phases. Note that the metallic atom
displacements portrayed in Fig. 8.15 are equivalent to type B displacements
(Fig. 8.4).
In the reciprocal lattice the formation of an MeX-type superstructure is
accompanied by the appearance of a system of new sites at the points "'1 + hi,
where hi stands for the vectors of the reciprocal f.c.c. lattice (Fig. 8.16). We
write down the expression for the structural amplitude. Preliminarily, it is
convenient to write down the coordinates of atoms and their displacements in
the coordinate system (x', y'), which is related to the MeX superstructure unit
262 CHAPTER 8
_I_l~ ,\
Gi l __LL I
I
y
j-, ~ 0 1\ ,I
A
1\ I -.!..\, f ;)
V1 w~ i ~ r
K ~ 0
_JJ_LL1L_
/
/ I
\ I
I
,
I I
I ,
I
Gs. lLLU ,
I .J;LF 0
I
~l ~V
t 'V
Y ~ '{ 'f ~
LLJ __
I
l_J~ G:l.
Fig. 8.14. Possible versions of the evolution of diffraction pictures at

reconstructive phase transitions.
Fig. 8.15. Projection of the b.c.c. structure on the (001) plane. 0,

metallic atoms; • and 0, interstitial atoms. The arrows show displace-
ments of metallic atoms. The dashed line shows the unit cell of the
superstructure.
cell edges:
Me: (O,-D.,O), (!,D.,!), (O,!-D.,!), (!,!+D.,O);
(30.4)
X: (~,~, 0), (~,~, 0), U,~, !), (~,~, !).
Then the following expressions may be written for the structural amplitude [2]:
F(hkl) = FMe(hkl) + Fx(hkl),

(30.5)
fMe, fx being the atomic scattering amplitudes and h, k, I the indices of the
reciprocal lattice sites in the (x', y') coordinate system.
Fig. 8.16. Primitive vectors of the reciprocal f.c.c. lattice.
The evolution of different reciprocal lattice sites with increasing displace-

ments ~ may be traced in two ways. One way is by exploring the dependence
of the intensity of each reflection on the magnitude of displacement ~. As a
result, reflections may be chosen that will become extinct when a critical value
of displacements ~c is reached. The rest of the reflections contain information
about the symmetry of the martensitic phase G 2 and about the orientation
relations.
The other way is to analyze the general form of the expressions (30.5)
with the view of determining the critical values of displacements ~c at which
a certain group of reflections may become extinct. The quantity ~ is involved
only in FMe. Therefore, on reaching critical ~ = ~c, the extinction condition
F( hkl) = 0 holds only for those h, k, and I for which the component Fx (hkl) =
O. The requirement Fx(hkl) = 0 allows two subsystems to be isolated from the
total set of reflections described by the expressions (30.5). These subsystems,
FI(hkl) and F2(hkl), are
FI = 2fMee-i4'Trn2fl (1 _eiS7rn2fl);
h = 2nI + 1, k = 2n2, 1= 2n3; (30.6)
F2 = 2fMee-i27r(2n2+I)fl (1 + ei47r (2n +I)fl);
2
h = 2nI + 1, k = 2n2 + 1, 1= 2n3 + 1.
The rest of the reflections describe the scattering from metallic and interstitial
264 CHAPTER 8
atoms and may be broken up into four types [2]:
Fa = 2fMee-i47rn2t!. (1 + ei87rn2t!. ) + 4fx;

h=2n1, k=2n2, 1=2na, n1+n2=2m;
F4 = 2fMee-i47rn2t!. (1 + ei87rn2t!. ) - 4fx;
h = 2n1, k = 2n2, 1= 2na, n1 + n2 =
2m + 1; (30.7)
F5 = 2fMee-i27r(2n2+1)t!. (1- e (2n +1)t!.) + 4ifx;
i47r 2
h = 2n1, k = 2n2 + 1, 1= 2na + 1, n1 + n2 2m; =

F6 = 2fMee-i27r(2n2+1)t!. (1-
e i47r (2n 2+l)t!.) - 4ifx;
h = 2n1, k = 2n2 + 1, 1= 2na + 1, n1 + n2 = 2m + 1;
where n1, n2, na and m are integers. The relative position of these six reflection
types is shown in Fig. 8.17.
2 6
t-_,_
-.
J.
z
-0
Fig. 8.17. Six sets of Fi (hkl) reflections.
Consider the reciprocal lattice sites belonging to the subsystem F2 . The

extinction condition for these sites is of the form
Ll- 12m + 1 (30.8)

- 4 2n2 + l'
The requirement that the displacement Ll be small (Ll ~ 1) limits the set of
possible m and n2 values: 12m + 11 ::; 12n2 + 11- As a function of the values of
m and n, the critical displacements are equal to t,
112 , 210' etc. Each such Llc
has its own period, which specifies the extinct subsystem of sites. For example,
~c = /2 corresponds to m = 0, n = 1. The sites that become extinct are

then numbered by the index k = 2n2 + 1 = 3. The site extinction period is
~k = 212n2 + 11 = 6. The extinction period characterizes the periodicity of
the reciprocal lattice of the final phase G2 along the corresponding direction.
The smaller ~c the larger the period ~k. As the reciprocal unit cell of the
phase G 2 increases in size, the Bravais unit cell in the direct space decreases
in size. It is evident that the volume of the phase G 2 Bravais cell should not
be less than the volume v per atom in the parent structure. Consequently, the
maximal size of the reciprocal unit cell in the b.c.c. structure is limited:
(30.9)
The condition (30.9) bounds from below the value of critical displacements:
~c min = 112 , The system of reciprocal lattice sites that corresponds to ~c min is
depicted in Fig. 8.18, where extinct sites are marked with crosses. To identify
the lattice type of the final phase G2 by the system of sites that remains, we
have to allow for the fact that the structural amplitudes degenerate at ~c = /2'
Fig. 8.18. Relative orientation of the f.c.c. and h.c.p. reciprocal

lattice; *, extinct reflections; 0, remaining reflections.
Substitution of ~c = 112 into the expressions (30.6) and (30.7) yields
F1(n2) = iF2(n2 + 1),

F3(n2) = -F4(n2 + 3) = -F5(n2 + 4) = iF6(n2 + 1). (30.10)
266 CHAPTER 8
The resulting equations imply that the intensities of the corresponding reflec-
tions are equal in magnitude (Ii '" IFi 12 ), the intensity of each of the reflections
F3 - F6 taking on four different values. As a result, the relative position of the
reflections that remain and their intensity prove typical for the h.c.p. struc-
ture. Figure 8.18 shows the orientation of the h.c.p. reciprocal lattice relative
to the initial f.c.c. lattice. The obtuse angle of the hexagonal cell which has
been obtained on the basis of only displacements ~, without taking account of
the homogeneous deformation, is equal to '" 109 0 • Therefore to obtain an ideal
h.c.p. structure, allowance must be made also for the homogeneous deforma-
tion of the reciprocal lattice, as was the case in analyzing atomic displacements
at the b.c.c. - h.c.p. transition (Fig. 8.8). The interrelation between the unit
cells of the b.c.c. and h.c.p. phases is demonstrated in Fig. 8.8.
31. Thermodynamic Analysis of the Homogeneous State
DESCRIBING THE MARTENSITIC TRANSITION IN TERMS OF DEFORMATION
The thermodynamic description of every phase transition is based on the de-

termination of the OP and its transformation properties. For this reason, we
start by ascertaining which of the strain tensor components describe the b.c.c. -
f.c.c. and b.c.c. - h.c.p. transitions considered in the foregoing. We begin with
the b.c.c. - f.c.c. transition. The fundamental and extra atomic displacements
at this transformation are sketched in Fig. 8.19. To determine the strain tensor
components corresponding to the fundamental and extra displacements, it is
necessary to write the relevant displacement fields [18]. Figure 8.19 presents
projections of fundamental and extra displacements on the (001) plane. The
displacement fields corresponding to Fig. 8.19 may be represented as
(31.1)
for fundamental displacements (type A) and as
Ux 2 = ~2(X - y), Yy2 = -~2(X - y), Uz 2 = 0, (31.2)

U x3 = 0, y = 0, z = ~3Z,
U 3 U 3
for the extra displacements. The last line describes the displacement field
corresponding to additional atomic displacements along the z axis at the b.c.c.
- f.c.c. transition; these displacements are shown by dotted arrows in Fig. 8.5.
From the definition of the strain tensor components, it is then easy to find the
corresponding components
fxx,l = -.6. 1 , = .6. 1 ,

fyy,l = 0,f zz ,l = = = 0; f xy ,l fxz,l fyz,l
fxx,2 = .6. 2 , = .6. 2 ,

fyy,2 = 0,
fzz,2 = .6. 2 ,
fxy,2 = = 0; fxz,2 fyz,2 (31.3)
fxx,3 = = 0, fyy,3 = .6.3 ,
fzz,3 = = = O. fxy,3 fxz,3 f yz ,3
We rewrite the expressions (31.3) in the system of cordinates x' = x + y and

y' = -x + y:
fxlx',l = -.6. 1 , = .6. 1 ,
fylyl,l = 0, fzlzl,l fx'YI,l = .6. 1 , f y lzl,l = fx l z l ,l = 0;
fXIX',2 = .6. 2 , =
fylyl,2 = 0, =
fZIZI,2 fx'YI,2 =
fX ' Z I ,2 f y lZI,2 = 0; (31.4)
f X ' X I ,3 = = 0,
f y l y l ,3 = .6.3 ,
f ZIZI,3 = f x ' y l ,3 =
fX ' Z I ,3 fy l zl,3 = O.
The expressions (31.4) tell us that the fundamental displacements correspond to
shear strain, and the extra displacements correspond to compressive or tensile
strain.
(a) (b)
Fig. S.19. Projection of atomic displacements at the b.c.c. - h.c.p.

transition on the (001) plane: A-type displacements (a) and extra
displacements (b).
Similarly, we explore the b.c.c. - h.c.p. transformation pictured in Fig. S.S.

Major displacement types at b.c.c. - h.c.p. transitions are type B displace-
ments. It is convenient to represent these in the projection on the (001) plane
268 CHAPTER 8
in a somewhat different form, the way they are shown in Fig. 8.20. As can
be readily seen from the formulas (5.1)-(5.6), the type B displacement field
portrayed in Fig. 8.20 is described by the optical mode of the IR T4 with the
wave-vector", = ~b3 (where b 3 is the reciprocal lattice vector) of the group
O~. Extra displacements at the b.c.c.-h.c.p. transition, similar to those in the
case of b.c.c.-f.c.c. transformations, are described by strain tensor components
fa{3,2,3 (31.3).
Fig. 8.20. Projection of B-type displacements participating m the

b.c.c. - h.c.p. transition on the (001) plane.
THERMODYNAMIC POTENTIAL AND PHASE DIAGRAM
We wish to construct a thermodynamic potential for the case of a b.c.c. - f.c.c.

transition. According to the expressions (31.3), we should take as the OP all
the six strain tensor components. It is convenient to pass over to symmetrized
combinations (see equations (21.6) and (21.7)):
1
el = "3(fxx + fyy + fzz );
e2 = V3( fxx - fyy), (31.5)
Disregarding the change in volume, the thermodynamic potential dependent

on e2,"" e6 has the form (see formulas for invariants (21.11) and (21.12))
if:
'I' = 1'1- (2
e2 + e32) + 1'2
- (2e4 + e52 + eii") + 3we3
1 - (2
e3 - 3e22) +
+W2e4e5e6 + o-[V3e2(e~ - e~) - e3(2d - e; - e~)]+

L (2
+4U1 e2 L (2
+ e32)2 + 4U2 L (e42 e52 + e42 e62 + e52 e 62) .
e4 + e52 + e62)2 + 4U3 (31.6)
This potential corresponds to a cubic symmetry and contains various versions

(domains) ofb.c.c. - f.c.c. rearrangement. Consider the transition correspond-
ing to the choice of the displacements (31.1) and (31.2). Expressing the para-
meters ei in terms of the strain tensor components (31.3), we proceed to the
effective potential for dimensionless shear and compressive strains, p = D"1/01O
and ~ = .D.2/.D.20:
<P = 1'1p2 + 1'2e - 31e + a-~p2 + 4p4

1 1
+ 4~4. (31. 7)
Here we have introduced the dimensionless parameters
(31.8)
where .D.20 = wu2'l, .D.1o =

w(u~ih)-1/4 and the renormalization of the po-
tential <P = ~¢ is determined by the quantity ¢ = u~w-4. In deriving the
potential (31.7), the change in volume was disregarded; this is equivalent to
the condition 2.D.2 = -.D.3, which allows the strain .D.3 to be excluded.
Note the crude character of the approximations incorporated in the poten-
tial (31. 7), which we intend to use for a qualitative description of the martensitic
transition. First, the potential contains lowest strain expansion terms that are
not really small quantities at such transitions, therefore the resulting potential
may be applied to describe only the pretransient state in the b.c.c. phase.
Nevertheless, in view of the symmetry being taken into account fully enough,
the potential qualitatively reflects the behavior of the system also below the
martensitic transition point. Second, the change in volume is substantial at
martensitic transitions. In neglecting the volume change we disregard the in-
ternal stresses that arise at the transition and affect the transition kinetics.
Nevertheless, we believe that the use of so crude an approach helps us to un-
derstand the most striking manifestations of the thermodynamics of martensite
transformation and the effect of external fields on this transition.
We construct the phase diagram corresponding to the potential (31.8).
The equations of state
p(21'1 + 2a-~ + p2) = 0 (31.9)

21'2~ - e + a-l + e = 0
have solutions describing three phases:
Phase (00): p = 0, ~ = 0;
Phase (~O): e - ~+ 21'2 = 0, P = 0; (31.10)
Phase (~p): e - e + 21'2~ + a-p2 = 0, p2 = -21'1 - 2a-~.
270 CHAPTER 8
We determine the stability regions of these phases. The stability conditions for
the phase (00) are described by the inequalities r1 > 0 and r2 > O. For the
phase (eO) we have the expressions for the OP:
(: - 1
"-2
+ (14 _ 2r 2 )1/2 , (31.11)
from which we determine the region in which the value
(31.12)
is real and the stability region is
(31.13)
The (00) -+ (eO) transition line is found from the condition that the energies
of the phases be equal in magnitude, <1>(00) = <1>(eO), and has the form
r2 = 1/9. (31.14)
The phase transition lines (00) -+ (ep) and (eO) ;::: (ep) were found numerically
and the final form of the phase diagram for the cases (7 0.5 and (7 =
-0.5 =
is given in Fig. 8.21. The potential is treated similarly in the theory of quasi-
crystals (see §42).
'~
Ai
G = 0.5
(00 )
- - - ----::-7
!! 2
~ ~
Uf)
Fig. 8.21. Phase diagram for (7 = ±0.5. The solid lines refer to first-
order transitions; the dashed lines refer to second-order transitions.
BEHAVIOR IN AN EXTERNAL FIELD
We now consider the properties exhibited by crystals undergoing martensitic

transitions in external fields. To this end, we must add to the potential (31.7)
-7f-~
C.;-- - -7fY-
~~ f
('--/-- ~ J
,[<i T~()
J 6 1
Fig. 8.22. Shape of the P1(0 function at different values of the para-
meter r2.
e
terms of the form -P1 and -P2 p. When the applied stress is conjugate to the
parameter e, the condition that the potential be minimal yields
e - e + 2r2e + crp2 = P1 (31.15)

p(p2 + 2cre + 2r1) = O.
In the phase (eO) the P1 (e) relation takes the form
P1 = e - e + 2r2e· (31.1G)
The shape of the function P1 is shown in Fig. 8.22. For r2 > ithe function P1
has no point of inflexion (Fig. 8.22b). In the interval ~ < r2 i
< the function
P 1 has extrema at the points (Fig. 8.22b):
e± = "31 ± (1"9 - 2 ) 1/2

"3 r2 . (31.17)
In this interval segments of negative slope arise on the right-hand wing of the
function P1 (0. Consequently, on reaching a certain value of P1 , a first-order
phase transition characterized by a hysteresis loop should take place in the
crystal (see §25). At r2 = ~ the function P 1 (e) is tangent to the abscissa axis
at the minimum point. Finally, the shape of the function P1 (e) for r2 < ~ is
shown in Fig. 8.22d,e,f.
272 CHAPTER 8
For the phase (ep) it is convenient to represent the expression (31.15) as
P{ =e-e+2r;e, (31.18)
p2 = -2(O"e + rd,
where P{ = =
PI + 0"1'1 and 1'; 1'2 - 0"2. The shape of the function P{ (e) is the
same as that in the previous case. A point of dissimilarity is that the condition
(p2 = 0) as a function of the parameters 1'2, 1'1 and 0" separates the region of
e
all values of into two intervals, one with p2 > 0 and the other with p2 < O. In
e
the first interval (p2 > 0) the P{ versus curve is described by the expression
(31.15), while in the second interval (p2 < 0) the relation is described by the
expression (31.16). On the boundary of these intervals the function PI (e) has
a cusp.
Consider the case where the external field is conjugate to the parameter
p. From the condition that the potential be minimal, we obtain
P2 = p3 + 20"pe + 2rlP, (31.19)

2 1 3 2
P = --(e - e + 2r2e)·
0"
By contrast with the previous case, the function P2 (p) is symmetric under
the replacement P2 -> -P2, p -> -po The function P2(p) has been explored
numerically for different values of the parameters 1'1, 1'2 and 0". Figures 8.23
and 8.24 depict the variation of the function P2 (p) with decreasing temperature
for 0" > 0 and 0" < O. Negative-slope segments denote instability of the crystal
over a given interval of P2 and p values (see §25) and indicate that the phase
transition is of first order. The broken lines in Figs. 8.23 and 8.24 show the
hysteresis loops that correspond to these first-order transitions.
As can be seen from Figs. 8.22 and 8.24, crystals undergoing martensitic
phase transitions respond differently to the different deformation types PI and
e
P 2 . Recall that the stress PI is conjugate to the parameter associated with
compressive strains, while the stress P2 is conjugate to the parameter p that
is associated with shear strain. The dependences P 1 (e) and P2 (p), obtained
within the framework of the two-component potential (31.7), may be qualita-
tively described by two models of one-component potentials. It can be readily
shown that a potential of the form
(31.20)
leads to the same dependences PI (e) as those presented in Fig. 8.22, while a
potential of the form
(31.21)
}'--.,.....
• .P
Fig. 8.23. Variation of the shape of the P2(P) function at (J" > 0 as
the temperature is lowered.
----.1'----1
+-~l-_f_7· /
Fig. 8.24. Variation of the shape of the P2(p) function at (J" < 0
as the temperature is lowered. The difference of the external field
effect on strain at (J" < 0 lies in the P2 (p) relation exhibiting S-shaped
anomalies.
274 CHAPTER 8
qualitatively describes the P2(p) relations obtained above. In the literature,

different authors employ these two forms of one-component potentials to ac-
count for various aspects of martensitic transitions. In [19,20]' for example,
the potential <1>2 is used to explain the shape memory effect and experimental
curves describing the applied stress dependence of crystal deformation. The
potential <1>1 is used for describing the pretransient state [21]; it is employed
also in [22,23]. The phenomenological potential (31.7) proposed by us involves
both potentials <1>1 and <1>2 as particular cases.
The choice of a particular potential (<1>1 or <1>2) as the simplest model is
dictated by which of the strain tensor components is viewed as driving in a
given transition. If the shear strain p is regarded as the principal component,
it is possible, by eliminating the compressive strain ~ from the potential (31.7),
to obtain the potential <1>2. Conversely, if one regards the strain ~ as the leading
component, one can, on excluding the parameter p, obtain the potential <1>1.
As we saw from the geometry of the foregoing versions of martensitic
transitions, both types of deformation, shear strain and compressive strain,
turn out to be involved in the transition. Therefore exclusion of one of these
strain types makes the description of the martensitic transition in terms of
Landau theory still cruder. The importance of preserving both deformation
types manifests itself also in the description of the inhomogeneous states of the
system.
SHAPE MEMORY EFFECT
The shape memory effect implies the ability of certain distorted-shape alloys
to recover their original shape spontaneously as the external conditions are
changed [24]. Examples of such alloys are Cu-20.4Zn-12.5Ga (at.%), Ag-45Cd
(at .%) and Cu-39.0Zn-4.6AI (at .%). The essence of the original shape -+
distorted shape -+ original shape cycle is elucidated by the diagram presented
in Fig. 8.25 [25]. At the first stage of this cycle an austenitic phase of a given
shape is cooled down to the martensitic transformation temperature. At the
point T = Tm a martensitic phase transition takes place as a result of which
the initial (austenitic) phase is replaced by a new (martensitic) phase. The
martensitic phase arises in the form of domains. The volume of each domain
differs from the volume of the corresponding amount of austenite; however,
since these domains are appropriately aligned relative to one another, the shape
of the entire sample changes insignificantly. All domains are iso-energetic. By
applying pressure to such a sample, we disturb the energy equality of different
domains, whereby the entire sample passes to a single-domain state. As a

result, microscopic changes in the volume of each domain add constructively
and bring about a substantial change of the entire sample. On removal of the
applied stress, the sample remains in the single-domain state, the shape of
the sample being distorted. To restore the original shape, it suffices to heat
the sample to the martensitic transition temperature at which the sample is
converted to the initial phase and recovers its original shape.
In,,",)- J'mc.;l1
m",~I(n" Ie
/Iud (n, fe ~~"'(/I/II'

I'h~ l'e
~~k~~C:-c'
'T11iI1~~V~~illli
t
--L - - --1,--
Ht:tl.Lng- ~ ioaoi;'I1f}
1111111111111[1 ~
ill UnevvJ, ~g-
1IIIIIIIIIIIIIIIi
\-----1--1
1--L-t:.L --L -ilL
'::"nlJfe -doma;Y/ S;'l1aee -Joft,""'n
'marfenr," .. rn"~ te"r ife
Fig. 8.25. Shape memory effect
32. Inhomogeneous States in the Vicinity of the Phase Transition
THERMODYNAMIC POTENTIAL WITH GRADIENT TERMS
To describe inhomogeneous states of a crystal undergoing a martensitic phase

transition, we proceed from a maximally complete description of the system in
terms of strain. Alongside the six components of the symmetric strain tensor
fOl(3, we introduce the antisymmetric rotation tensor wOl (3, defining these tensors
in the standard way [18]:
_ 1 (auOl aU(3 ) _ 1 (auOl aU(3 )

fOl(3 - '2 aX(3 + ax Oi ' wOl(3 - '2 -a
x(3 - -a
XOi .
(32.1)
With the crystal as a whole rotated homogeneously, the energy of the crystal
should not change. Therefore, the thermodynamic potential is independent
276 CHAPTER 8
of the tensor components wOl {3, but it may depend on their derivatives, which
should be included when writing down the gradient terms.
Also we need to invoke the compatibility equations coupling the tensor
components fOl{3 and WOI{3. This is because not all of the tensor components
are independent, for they are expressed in terms of derivatives of the three-
component quantity U OI ' that is, the displacement vector. Mathematically,
these relations follow from the condition that the mixed derivatives be equal
in magnitude:
U OI ,{3-y = u OI ,-y{3' (32.2)
Physical compatibility conditions arise from the requirement that displacement

fields u OI ( r) may be constructed using given strain fields.
Differentiating the expression (32.1) and using the relation (32.2), we can
write the compatibility condition in the form
W OI{3,-y = fOl-y,{3 - f-y{3,OI' (32.3)
Elimination of W from this expression gives the relation between the second-
order derivatives of the strain tensor components only:
f Ol{3,-y6 - fOl-y,{36 - f6{3,-y0i + fD-y,{301 = 0.. (32.4)
By contracting two subscripts, we obtain one more relation:
f Ol{3,-y-y - fOl-y,{3-y - f-y{3,-yOi + f-y-y,{301 = 0, (32.5)
called the compatibility condition. In explicit form, this equation splits up into
six equations:
fxx,yy + fyy,xx = 2fxy ,yx;
fxx,zz + fzz,xx = 2fxz ,zx;
fyy,zz + fzz,yy = 2fyz ,zy;

(32.6)
fxx,yz + fyz,xx = fyx,xz + fxz,zy;
fyy,xz + fxz,yy = fxy,yz + fyz,xy;
fzz,xy + fxy,zz = fxz,yz + fyz,xz·
However, only three independent equations remain [26]. Using equations (32.3)
and (32.6), we may eliminate w from the gradient invariants of the thermo-
dynamic potential and find the independent invariants. Homogeneous invari-
ants' for the cubic group in terms of the symmetrized combinations (31.15)
transforming according to two-dimensional and three-dimensional IR's are writ-

ten out in the expansion (31.16). Trivially, we could here add terms that de-
pend on the volume strain el, which is an invariant. The complete fourth-order
expansion has the form
<Ph = rlei + r2(e~ + e~) + r3(e~ + e~ + e~)+

+Vl ef + V2el (e~ + e~) + V3el (e~ + e~ + e~) + V4e3( e~ - 3e~)+
+v5e4e5e6 + v6[e3(2e~ - e~ - e~) + v'3e2(e~ - e~)]+
+ulei + u2ei(e~ + e~) + u3ei(e~ + e~ + e~) + u4(e~ + e~)2+
+u5(e~ + e~ + e~)2 + u6(e~ + e~)(d + e~ + e~) + u7ele3(e~ - 3eD+
(32.7)
The gradient-dependent part <Pinh of the potential can readily be shown

to consist of six second-order invariants in strains:
<Pinh = ~ J
dr{ alel~el + a2(e2~e2 + e3~e3)+
+d3el(~2e2 + ~3e3) + a4(e3~3e3 - e2~3e2 - 2e3~2e2)+
+d5(e4~e4 + e5~e5 + e6~e6)+
+a6(e4~5e6 + e5~6e4 + e6~4e5)}. (32.8)
Here we have introduced the notation for the differential operators
(32.9)
which transform according to the same IR as the quantities el, ... , e6 (31.15)
do.
EQUATIONS OF MOTION
The particle motion in the crystal is determined by the Lagrange equation
6L d 8L
(32.10)
8uO/ - dt 8uO/'
278 CHAPTER 8
where the Lagrangian function L = T - eI> depends on the displacements in the

kinetic part and on the strains in the potential. Evidently,
(32.11)
and the potential eI> is determined by the sum of the expressions (32.7) and
(32.8). The equation (32.10) may now be rearranged to read
.. 8eI>
pUO/ = --c-' (32.12)
uUO/
where the variational derivative with respect to displacement is taken with

allowance for the fact that the potential eI> depends only on derivatives with
respect to displacements, that is, on strains, so that
The explicit form of the Lagrange equation may be obtained by writing out
the variational derivative of the potential with respect to strains:
8eI> 0<jJ 0 8<jJ 02 8<jJ

(32.13)
8fO/(3 = Of 0/(3 - OX'"( 8fO/(3,'"( + OX'"(OX(3 8fO/(3,'"(0 + ... ,
<jJ being the density of the functional eI>.
We see that the equation of motion (32.12) contains two types of quantities,
namely, strains and displacements. If we wish to have an equation made up
of variables alone, that is, strains, we must differentiate equation (32.12) with
respect to the coordinate.
For the potential described by the expressions (32.7) and (32.8), the ex-
plicit form of the Lagrange equations is too complicated. We consider therefore
some particular cases where only one of the three OP's is taken into account.
Specifically, allowance is made for either the two-component OP (e2e3), which
describes tetragonal strain, or the three-component OP (e4e5e6). In these par-
ticular cases we can obtain localized solutions to the equations of state, that
is, solitons, which describe the motion of the boundaries of different phases
corresponding to the thermodynamic potential introduced.
TETRAGONAL-STRAIN PHASE TRANSITION
Consider a tetragonal to cubic phase transition with a two-component strain

OP (e2e3). Such a phase transition occurs in A-15 compounds. Assume that the
Fig. 8.26. Shape of the thermodynamic potential (32.17) as a func-

tion of the OP p for two temperatures - above and below the phase
transition temperature.
rest of the strains are absent in the entire crystal, that is, el = e4 = es = e6 = O.
Suppose also that the state of the crystal remains homogeneous along the z axis.
The general compatibility equations (32.6) here reduce to
82e3 82e3 8 2e3 ( 82 82 )
8x2 = 8y2 = 8x8y = 0, 8x2 - 8y2 e2 = O. (32.14)
The equations (32.14) determine the character of the solution:
e3 = const, e2 = f(x + y) + i(x - y). (32.15)
The thermodynamic potential is a functional of the form [27]
1> = ~ Jdr{r2(e~ + e~) + v4e3(e~ - 3e~) + u4(e~ + e~)2+

+a2(e2~e2 + e3~e3) + a4(e3~3e3 - e2~3e2 - 2e3~3e2)}' (32.16)
where e2 and e3 depend only on the coordinates x and y. The homogeneous

part of the potential 1> describes a first-order transition due to a cubic invariant
(see §17). In terms of the modulus-phase variables (e2 = =
P sin ¢J, e3 P cos ¢J)
the homogeneous part is
(32.17)
Minimization with respect to ¢J yields three values of the phase, ¢J = 11', 11'/3,
and -11'/3 (for definiteness, we assume that V4 > 0), which correspond to the
elongation of the crystal along one of the cube axes. Minimizing with respect
to P, we determine the phase transition point rc = VV4U4, the OP Po jump
at this point and the temperature dependence of energy as a function of the
OP (Fig. 8.26). The phase transition from the initial cubic (p = 0) to the
tetragonal (p i 0) phase occurs when the potential's minimum 1>h(p) touches
the abscissa axis.
280 CHAPTER 8
We now write the equations of motion for the OP components, using the
general form (32.12) and the potential (32.16). We have
.. 82 82 8 8
pe2 = 3 ( -2 + - ) -
8x 8y2 8e2
v'3(-8~
- -)
-
8x 2 8y2 8e3
-8~2 2
(32.18)
.. 8 8 8 8
pe3 = -v'3(-2 - -)-+ (-+ -)-
2 8~ 2 8~ 2 2
8x 8y2 8e2 8x 2 8y2 8e3
Recall that the solutions of equations (32.18) must satisfy the compatibility
equations (32.15). We now take the form of the solution with e2 depending on
x - y:
e2 = e2(x - Y - vt) == e2(r).
For solutions of this particular form (allowing for e3 = const) equation (32.18)
reduces to
Choose the boundary conditions in the form
(32.19)
assuming the equilibrium conditions to be valid at r = ±oo. The strain equa-

tions then reduce to the following two equations
8~ = 0, (32.20)
8e3
where e20 = e2 (r -> ±oo).
The second of these equations may be represented as
2r2e3 + 3V4 e32 + 4u4e33 + 4u4e22 ( e3 - 3 V4) = 0 .

4" U4
For e3 to be a constant, we must require e3 = 3V4( 4U4)-1. Thereupon the

solutions of the equations give the quantity
(32.21 )
Only with this quantity is the condition e3 = const fulfilled. Thus the above
condition is fulfilled only at one temperature point. At all other temperatures
we have to relinquish the condition e3 = const.
The first of the equations (32.20) is explicitly an ordinary non-linear dif-

ferential equation:
2 27 v4 3 d2e2
v p(e2 - e20) = - - -e2 + 4U4e2 + 4(C¥2 + C¥4)-d
2. (32.22)
4 U4 T
Considering the limit T ..... ±oo, we see that if e2(+oo) 1= e2(-oo), then the
equation is satisfied only at v = O. Thus a domain wall at rest exists at temper-
ature (32.21) which separates two phases with e2(+oo) and e2(-oo) (Fig. 8.27)
[27]. These phases are two martensite domains with different tetragonal axis
orientations. The corresponding solution of equation (32.22) is
_ ± 3v'3 V4 hx- y- TO (: _ 4 (( C¥2 + C¥4)U4) 1/2

e2 - -4- - tan (: , .. - . /0 2 . (32.23)
U4 .. 3v 3 v4
\
\
\ Jl I
Fig. 8.27. Picture of the strain between two tetragonal-phase domains

oriented in the x and y directions [27].
From the formulas thus found we can reproduce the displacement fields.
The complete set of strain-tensor components in our case has the values:
(32.24)
From the first three equations we obtain expressions for the spatial derivatives
of the displacement vector:
ux,x = ~ [~e2(x - y) - ~e3]' Uy,y = -~ [~e2(x - y) + ~e3]' uz,z = ~e3.

Integrating these relations yields
1
Uz = 3e3z + l1(x, V),
1 1
Ux = 2v'3 F (x - y) - (ie3x + h(x, V),
1 1
uy = 2J3 F (x - y) - (ie3Y + h(x, V),
282 CHAPTER 8
where
F(x,y) = fo X
-
y
dte2(t) = C1'2~0:4r/2Incosh(X~Y)
and h, h and fa are arbitrary functions of their own arguments. The arbitrary
functions may be determined from the last trio of equations (32.24):
h(x, y) = const + C1X + C2Y,

h(x, y) = const + C3Y - C1Z,
fa(x, y) = const - C2Z - C3X.
These functions describe a trivial displacement and rotation of the solid as a

whole and may therefore be thrown away. Thus we obtain the following dis-
placement field corresponding to strains (32.24) conjointly with the expression
(32.23):
u x = uolncosh (
X -
-e-Y) -
'16 e3 x ,
(32.25)
u y = Uo In cosh (
X -
-e-Y) -
'16 e3Y,
where
Uo = _1_ (0:2 + 0: 4 )1/2.
2v'3 U4
Such displacements, giving rise to a natural conjugation of two domains with

a 90 0 polarization, are pictured in Fig. 8.27.
Unfortunately, the solution presented above applies only to one point of
the temperature interval in which the martensitic phase exists. Outside this
point both strains e2 and e3 become dependent on coordinates, a fact which
contradicts the compatibility equations (32.14). In this case one has to re-
linquish the condition that the four other strains be equal to zero, and the
resulting complicated system of equations has no known analytic solutions.
PHASE TRANSITION WITH SHEAR STRAIN
Now we consider a phase transition that is described by a three-component

OP made up of shear strains f xy , fxz and f yz . Suppose that a structure is
realized that is due only to one component, for example fyz =
e6; the two other
components correspond to domains of different orientation. Such a strain, as

we saw in §31, is a constituent part of the strain of the parent b.c.c. lattice as
the latter converts to an f.c.c. phase. In this section we will explore only an
isolated shear strain, setting
(32.26)
Taking into account the boundary conditions e6(Y = ±oo) = 0, the compati-
bility equations
{} 2e 6 _ {} 2e 6 _ {} 2e 6 _ {} 2e 6 _ 0
{}x{}y - {}y{}z - {}x{}z - {}y2 - (32.27)
in this situation allow a solution of the form
e6 = f(z) + j(x).
Thus we shall try to solve dynamic equations that depend only on one coordi-
nate z or x.
The potential (32.9) + (32.10) under the conditions (32.26) reduces to the
functional
(32.28)
To this functional we have added a sixth-degree term in strains, since we are

concerned with the possibility of describing a first-order phase transition (such
a possibility arises in the absence of a cubic term only when the coefficient of
the quartic term is negative). Thus we assume that the conditions (U5 + U10) <
0, a5 < 0 and w > 0 hold. It is convenient to go over to the dimensionless
coordinates
w
e = ( - u5 +w UlO ) 1/2 eo,
_ (_(U5+ U10)2)1/2
x- ,
wa5
in terms of which the functional (32.28)
F = J dxf(x), f(x) = re 2 - e4 + e6 + e/2 (32.29)
contains only one literal parameter r, that is, the temperature (the prime de-
notes the derivative with respect to the coordinate). This functional and the
associated dynamic equations have been investigated by Falk [28,29].
The homogeneous part of the functional fo = re 2 - e4 + e6 as a function of
the OP e exhibits different behavior in four temperature intervals (Fig. 8.28):
(a) r> 1/3. There is one minimum fo at the point e = O. This minimum
corresponds to the stable point of the austenitic phase.
t
(b) < r < ~. Two extra degenerate minima arise at the points eo. These
minima correspond to the metastable martensitic phase; the minimum e = 0
corresponds to the stable austenitic phase.
284 CHAPTER 8
(c) 0 < r < ~. As before, there are three minima, but the energy of the
martensitic phase becomes lower than that of the austenitic phase, which is
metastable in this interval.
(d) r < O. There are only two minima ±eo, which correspond to two
domains of the stable martensitic phase.
llL
\
o e e
- eo 0 eo)
(a) (b)
10 10
e
(c) (d.)
Fig. 8.28. Variation of the homogeneous thermodynamic potential fa

with temperature.
The equilibrium value of the OP eo varies with temperature at r < ~

according to the formula
eo = ± (
1 + VI
3
- 3r) 1/2 . (32.30)
Thus a first-order phase transition occurs at the point r 1/4. Above =

and below the transition temperature there is a region of hysteresis in which a
superheated martensite may exist at ~ < r < ~ and a supercooled austenite at
0< r < ~.
Now we set up the equation of motion. The kinetic energy T = pu 2 /2
may be represented in dimensionless form by introducing the dimensionless
time t 2 -+ W2(U5 + U10)-1(pa5)-1/2t. Account should be taken of the fact that
the potential energy depends on the quantities e and e', that is, on the first
and second derivatives of the displacements, since e = du/dx. We obtain the

Lagrange equation
.. _ d dlo 2 d 2 I
U - dx de - dx 2 e .
By differentiating the above equation with respect to x, we eliminate u and
bring the equation into a form that contains only one quantity, namely, the
strain:
e = (~: - 2e ll
)". (32.31)
The unusual character of this dynamic equation is due to the fact that the
potential energy of the model depends on derivatives with respect to the coor-
dinates (that is, strains) rather than the displacements.
\Ve try localized solutions of this equation in the form
e = e(x - vt), x - vt == T (32.32)
with the boundary conditions
x -> ±oo: eI = 0, dlo = o. (32.33)

de
The last relation implies that an equilibrium phase exists at infinity, that is,
e oo and e_ oo may assume the values 0, -eo and +eo. For a solution of the form
(32.32), equation (32.31) is an ordinary equation with respect to the variable
T. Integrating equation (32.31) twice with respect tOT, we arrive at
2 1/ dlo
v e + e - de = + Cl,
2
C2 Z (32.34)
where the prime now denotes differentiation with respect to T. From the bound-
ary conditions (32.33), we find
The last relation means that (a) e oo = e_ oo and Cl = v 2 eoo is a moving soliton
in one phase and (b) e oo ::p L oo , Cl = 0 and v = 0 is a domain wall at rest.
Integrating equation (32.34) with respect to de yields the integral of motion
(32.35)
where Fa is the integration constant. Using this equation we can readily write
1: 1:
the total soliton energy E corresponding to the solution
E= dx(T+F) = dx{2/o(e)-Fo +Cle}. (32.36)

286 CHAPTER 8
We find the localized solutions of equation (32.25) in the four different cases
determined by the boundary conditions.
(1) Domain boundary between the austenite and the martensite (e_ oo =
eo, e oo = 0, v = 0). The conditions e oo = 0 and e~ = 0 give Fo = O. From
the conditions Coo = eo and e~oo = 0, we find fo(eo) = 0, which is fulfilled at
the point r = ~. Thus an austenite-martensite domain wall at rest exists only
at the phase transition point. Under these conditions equation (32.35) reduces
to
(32.37)
The solution of this equation has the form
-1/2
e(x) = [2(1 + eX-XO) ] (32.38)
and the energy is calculated by the formulas (32.36) and is equal to E = ~.

No stationary solution of the form (32.32) exists if we withdraw from the
phase transition point. This means that the domain wall may move only with
an acceleration due to the energy difference of the two phases.
(2) Boundary between two martensite domains (e_ oo =
-eo, e oo =eo, v =
0). The boundary conditions give the constant Fo = - fo(eo) = fo( -eo), and
equation (32.35) becomes
(32.39)
The condition for a local solution to exist is e'2 > 0 over the entire range
-eo < e < eo, so that ei should be greater than zero; from this it follows
that r < ~. We arrive at the natural conclusion that the domain boundary
exists only below the phase transition point. The shape of the boundary is
determined by the solution of equation (32.39):
e(x)
X-Xo][ a + sinh 2 -~-
= [eo sinh -~- X-XO]-1/2 , (32.40)
where
3e 02 - 1
C 1 =eo(3e 6- 1)1/2, a= 22 l'
eo -
The width of the wall is determined not only by the quantity ~, but also by
the parameter a involved in the denominator. Specifically, when r --+ ~ (as
the transition temperature is approached) e6 --+ ~; therefore the parameter a
diverges, leading to an infinite wall width.
mf2iastQbfe
a L( s t e ni i e
o "-----------p> lJ2
Fig. 8.29. Stability region of the martensite soliton in the austenite

(shaded area) in the temperature-velocity plane.
(3) Localized martensitic region in the austenite (coo eoo 0, v 0). = = t=

In this case the constant Fa is equal to zero, and equation (32.35) takes the
form
(32.41 )
t=
For a localized solution to exist, we must have a value of e 0 such that e' = 0,
that is, a turning point must exist. This means that we must have e~ > 0 and
e~ > 0, whence the velocity v is included in the interval
- ~ + 21' < v 2 < 21'. (32.42)
Integration of equation (32.34) yields [28,29]:

e2
e(x,t) = 1/2' (32.43)
[1 + (1- eVe5)sinh2((x - vt - xa)/e)]
where
(V2) 1/2
e=
1
eZ e 3 = l' - 2"
is the inverse width of the soliton. The soliton stability region is shown in
Fig. 8.29. A soliton at rest may exist only when 0 < l' < ~, that is, in a
metastable austenite. In this temperature interval the soliton at rest may be
viewed as the nucleus of the new phase in the supercooled austenite. As the
velocity is increased the amplitude of the soliton decreases, and when v 2 = 21'
the soliton ceases to be a nucleus. Only moving solitons may exist in the stable
austenitic phase (1' > ~). The maximal amplitude here is reached at the lowest
velocity v 2= 21' - ~ and is equal to e~ =
~. As the velocity is increased
the amplitude decreases, and the width increases and diverges at the maximal
velocity v 2 = 21'.
288 CHAPTER 8
(4) Localized austenitic region in the martensite (e_ oo = eoo = eo, vi- 0).
The equation of motion becomes
(32.44)
whence we immediately see the tempreature constraint r ~ ~. A localized

solution exists if there is a turning point e = em at which e' = 0. The quantity
em is a root of the equation
2
(e + eo) (e + 2eo2 - "2
2 2 V
1) - = 0, (32.45)
this root being closest to eo. An analytic solution of equation (32.44) is difficult
to obtain since here we need to know the roots of the quartic equation (32.45).
In the metastable-martensite region (~ < r < ~) we can obtain a zero-velocity
soliton solution:
1 - 2efi ] 1/2
e(x)= [ . , (32.46)
1 - ((3efi - l)/efi) tanh 2 ((x - xo)/e)
where
For finite velocities as well as for the stable-martensite region, numerical solu-
tions of equation (32.44) have been obtained in [29].
We have considered separately the reconstruction of a cubic lattice due to
tetragonal and shear strains. As was shown in detail in §30, the martensitic
b.c.c. --+ f.c.c. transition involves both strains simultaneously and is described
by the general energy functional (32.7) + (32.8). The first approximate treat-
ment, however, may incorporate only fundamental displacements of type A
(Fig. 8.19a), which are described only by the shear strain in the system of
coordinates directed in the (001) plane along the lattice diagonals. Therefore
the solutions obtained under the restriction (32.36) may be a first step toward
a discussion of the inhomogeneous states at the b.c.c. --+ f.c.c. transition.
Since this approximation disregarded tetragonal strains (and also the change
in volume), the question of a complete description of this transition remains
open.
SQUARE LATTICE
The general functional for three-dimensional space is too complicated to
permit an understanding of all the regularities in the interplay of inhomoge-
neous strains. Therefore it is reasonable to go over to the two-dimensional case,
where the martensitic transition is modeled by the transition from the square
lattice to the triangular lattice (Fig. 8.30). The necessary displacements are
described by the following four strain tensor components:
el = ~(ux,x + Uy,y), e2 = ~(ux,x - Uy,y),

(32.47)
e3 = ~(ux,y + uy,x), w = ~(ux,y - uy,x).
The quantity el is the change in volume (area), e2 describes the strain along
one of the axes, e3 describes the shear strain and w describes the torsional
strain.
~~.--4'~'~-·~~
;, ~ ~
At..'" ~ ~
----:~: ~:-----..!---...:
Fig. 8.30. Geometry of the transition from the square to the triangular
plane lattice. The symbols are the same as those used in Fig. 8.5.
The condition that the mixed derivatives be equal in magnitude places

constraints on the inhomogeneous strains:
(32.48)
These constraints allow us to eliminate the derivatives of wand to write the

relations between different strain tensor components:
(32.49)
This equation is a particular case of the compatibility conditions (32.5) for the
two-dimensional space.
We write the thermodynamic potential in the form
 = J
dr¢(r), ¢(r) = ¢h + ¢inh(r), (32.50)
290 CHAPTER 8
where
'l'h
A-.
= rl e2
l + r2e2+ r3e3+ weI + Ul el + U2 e2+ U3e3+
223444
+O"lele~ + 0"2ele~ + 2Vleie~ + 2V2eie~ + 2V3e~e~, (32.51)
[( ae 1 2 2
</Jinh(r) = 11 ax )2 + (ael)2]
8Y [(ae
+ 12 ax )2 + (ae
ay )2] +
ae3)2 + (ae3)2]
+/3 [( - -ay + vI [ael
i: ae2 ael ae2]
-- - - (32.52)
ax ax ax ay -ay .
Thus only four inhomogeneous invariants are independent. The other three
invariants
ael ae3 + ael ae3 (aW)2 + (aW)2 ow ae3 _ aWae3

ax ay ay ax' ax ay' ax ax ay ay ,
which we could write by symmetry considerations, are expressed as a linear
combination of these four terms. This is easy to verify using equation (32.48).
We write the Lagrange equation for the displacements
(32.53)
To start with, we explore the possibility of static localized solutions appearing

in the case where the quantity </J is independent of one of the strains. Let
o</J/bel = O. The Lagrange equations then assume the form
a 8</J a o</J a 8</J a o</J
ax oe2 - ay oe3' ay 8e2 - ax 8e3 .
Virtually, these are the Cauchy-Riemann conditions for the function 1/J =
o</J/oe3 + io</J/8e2 of the variable z = x + iy to be analytic. Being bounded on
the entire z plane (xy plane), the function 1/J is a constant, that is, O</J/8e3 = c
and O</J/8e2 = c'. The boundary conditions at infinity yield c = c' = O. As a
result, we obtain the equations
!:!:...
8e3
= 0, (32.54)
which reduce to the thermodynamic-potential minimization equations. Anal-

ogous results are obtained when the potential </J is independent of either the
strain e2 or e3' The equations (32.54) in the two-dimensional case are too
complicated:
0
(oxcj22 + Oy2)
2 3 2
13 e3 = r3 e3 + 2U3e3 + 2v3e2e3.
In the completely isotropic case,
r2 = r3 == r, 12 = 13 == I' U2 = U3 = V3 == U,
this system reduces to a two-dimensional non-linear Schrodinger equation for
(32.55)
This equation was used earlier in the theory of vortices in a non-ideal Bose gas
[30]. The above equation was shown to have vortex solutions, which in our
case describe a localized austenitic region in the martensite. Indeed, at infinity
the function 1/J tends to the equilibrium value 11/J12 = e~ + e5
= r/2u, while at
the center of inhomogeneous distribution (r = 0) it has an asymptote 1/J '" r V ,
where v is an integer specifying the azimuthal dependence of 1/J.
We now investigate the solutions in which two of the four strains el, e2, e3
and ware equal to zero in the entire plane. In four cases,
el = w = 0, e2 = w = 0, e3 =w = 0 and e2 = e3 = 0,
the minimization equations yield homogeneous solutions for two extra strains.
In two cases, el = e2 = 0 and el e3= =0, a localized plane solution arises,
either in the direction of the edge of the parent-lattice square or in the direction
of the diagonal. For example, el = e2 = 0, w = e3 - 20',
(32.56)
A similar solution with e2 replaced by e3 and with x replaced by (x + y)/V2

was obtained in [31]. It is easy to see that this solution describes the domain
boundary between two distinct domains of the martensite phase and is a two-
dimensional analog of the boundary between two domains of the tetragonal
292 CHAPTER 8
structure (32.23) in the three-dimensional case. The simplifications made in

going over to the two-dimensional lattice permit us, however, by contrast with
equation (32.23), to obtain a solution at any temperature below the transition
temperature.
We sum up what has been said above. The partial solutions that have
been obtained in this section describe some aspects of the problem of marten-
sitic transformations in crystals. Thus the derived solutions of the equations
for strains (32.23), (32.40) and (32.56) such as domain walls give a descrip-
tion of the region of twinning at martensitic phase transitions, which are an
alternative to the dislocation model. Other solutions, (32.43) and (32.46), are
localized states. These solutions may be interpreted as critical nuclei in the
metastable state. A remarkable feature of these solutions is the velocity de-
pendence of the temperature interval in which nuclei exist. This feature leads
to the possibility of martensite nuclei arising above the phase transition tem-
perature. However, describing pretransient phenomena, usually pronounced in
martensitic transformations, calls for an analysis of the solutions of the com-
plete model (32.7) plus (32.8), which takes into account all the strain types,
namely, shear, tetragonal, and volume strain. We should bear in mind that this
"complete" model too is a limited one, as it employs an expansion in powers
of strains. Besides, other degrees of freedom, associated, for example, with op-
tical displacements and electronic states, may also be essential in real crystals
undergoing martensitic transformations.
33. The Omega Phase
INTERRELATIONSHIP BETWEEN THE LATTICES AT THE b.c.c. - w-PHASE

TRANSFORMATION
In the foregoing we considered mutual transformations of b.c.c., f.c.c. and
h.c.p. lattices. The b.c.c. --+ f.c.c. transformations were shown to be described
by strain tensor components. The b.c.c. --+ h.c.p. transformation is described
by the displacement mode corresponding to the wave-vector K, = !b 3 and by
compressive strains. The b.c.c. --+ w-phase transformation which we consider
below is described by the displacement mode only and requires no additional
strains (Fig. 8.31). In this sense the transformation of the b.c.c. structure to
the w-phase does not comply with the definition of martensitic transformations
(see §30).
The w-phase may be regarded as an intermediate phase at the reconstruc-
tive transition G1 --+ Gint --+ G2, where G 1 = O~ is the symmetry group of the
6~R~!
9
1'r / ! 0 _~
~
3 4·
(a) (b) (c)
Fig. 8.31. b.c.c.-w-phase transition: P 1 , P2 , and P3 planes in the b.c.c.

lattice (a), the displacement ofthe Pi planes at the transition (b), and
the unit cell of the w-phase (projection of the b.c.c. cell on the (111)
plane) (c). 0, atoms of the P 1 plane; *, atoms of the P2 plane; 0,
atoms of the P3 plane.
initial b.c.c. structure, Gint is the symmetry group of the intermediate w-phase,
and G 2 = D~h is the symmetry group of the final phase, called an ideal phase
or an aging w-phase [32]. The w-phase is realized in disordered quenched Zr-
and Ti-based alloys, as well as in Nb-Mo, Mo-Re, and other alloys [32].
According to X-ray structure analysis data, the w-phase is described in
various systems by either the wave-vector "'w = ~(111) or the wave-vector
'" = "'w + 8"', which is close to the former vector. In this context we wish to
note that since the point "'wis not a symmetric point of the reciprocal lattice,
the structure of the w-phase is independent of the wave-vector type ('" or "'w)
by which it is described. For definiteness, we will consider the vector "'w. Let
us reveal the IR's that describe the w-phase structure.
The wave-vector "'w = ~(b1 + b 2 + b 3 ) belongs to the eight-arm star {~7}
of the b.c.c. lattice [33]. The h.c.c. lattice contains one atom 1'1 = (000) per
unit cell. From the general formulas (5.1)-(5.3), we readily obtain that the
mechanical representation decomposes into two IR's of the group G"w'
(33.1 )
of which T1 is an identity representation and T3 a 2-dimensional representation.

294 CHAPTER 8
The modes of the representations 71 and 73 for the arms K-w and -K- w , found
by the formulas (5.5), are given in Table 8.1. The modes for the other arms
K-L of the star {K-7} are easy to find by the formula (5.6). The values of the
modes on the nth atom are determined by the expression
'!/JOt ( "LVI)
>. n >. I0)e'''Lt
= '!/JOt ("<tV . n, (33.2)
'!/JOt e In)
LV being the atomic component of the basis function in the nth cell.
Table 8.1
Displacement modes for group G" arms ±K-w
7 K- r1(0 0 0)
71 K-w 1 1 1
-K- w -1 -1 -1
K-w 1 (2 (
73
(2 1 (
_ (2 - (
-K- w -1
_ (2
-1 -(
where ( = exp( -27ri/3)
The structure of the w-phase is described by two modes 71 with arms ±K-w .
Since the vector K-w is parallel to the [111] axis, the displacements of all atoms
lying in the (111) plane are equal in magnitude. Therefore, the formation of
the w-phase may be viewed as resulting from displacement of (111)-type planes,
as shown in Fig. 8.31. Indeed, the atoms of the P1 plane are not displaced, the
atoms of the P2 plane are displaced by the amount u and the atoms of the P3
plane are displaced by the amount -u along the [111] direction. The resulting
structure of the w-phase has the symmetry D~d. On reaching the magnitude
of displacement u = a-/3/12, the atoms belonging to the P2 and P3 planes
emerge in the same plane (Fig. 8.31) and the symmetry of the crystal rises to
D~h. Figure 8.31c shows that no additional strain is needed to form an ideal
w-phase.
THERMODYNAMIC POTENTIAL
As the OP at the b.c.c. - w phase transition we may choose the mode mixing
coefficients T}1, T}2 for the IR 71. The form of the matrices of this representation
[33] determines the transformation properties of the components T}1 and T}2 and
the form of the invariants involved in the potential:
(33.3)
It is convenient to introduce the new variables, T}1 =

T}e;'" and T}2 = T}e-;'"
and to go over to the dimensionless form of the potential:
(33.4)
where
u - u3 u2 (33.5)
P=T}2iiJ' = (2iiJ)4' 7'=r(2iiJ)3'
From the condition 8/8<jJ = sin 3<jJ = 0 we find the equilibrium values of the
angle <jJ = 0, 7r /3, 27r /3. These three solutions correspond to three translational
domains which differ in the phase of displacement waves of (111) planes along
the [111] direction.
We set <jJ = 7r /3 and explore the form of the potential (33.4) at different
temperatures 7' = 7"(T-Tc). To this end, we investigate the condition 8/8p =
0, from which we find
(33.6)
The requirement that P± be real determines the temperature 7'1 = ~ at which

a point. of inflexion occurs on the versus p curve (Fig. 8.32). We write down
the value of the potential at the point p+ of minimum:
(33.7)
The condition min = 0 determines the first-order phase transition temperature

7'2 = i
(Fig. 8.32c).
One of the most remarkable features of the potential (33.4) is the presence
of a cubic term ~ p3. In consequence, when 7'2 < 7' < 0, the system described
by such a potential may be in the metastable state, thus being responsible for
the existence of pretransient states [32]. Indeed, alloys undergoing a b.c.c. -
w-phase transition exhibit strongly pronounced pretransient phenomena.
296 CHAPTER 8
Fig. 8.32. Variation of the (p) relation with decreasing temperature.
External effects on the b.c.c. - w-phase transformation are described by the

term"'" p2 P in the potential <1>. Such coupling of p and P comes from the fact
that the transition parameters p and ¢ are not macroscopic variables. Thus
the allowance for an external field leads to renormalization of the transition
temperature.
INHOMOGENEOUS STATES
We have explored a potential that corresponds to the wave-vector Kw = hb1+

b 2 + b 3 ). However, according to experimental data [32], the occurrence of the
phase is in a number of cases specified by wave-vectors close to Kw : K =
Kw + OK. To describe such a situation, gradient invariants should be added to
the potential (33.3). Consider the potential
i'*'i. -_ -1
V
J {iii. + - ~ (01]2
dr '*'w U ~
a=l
01]1) + 'Y- ~ -
1]1-- -1]2--
OXa OXa
~
01]1
-- 01]2
a=1 OXa OXa
-} (33.8)
and introduce the dimensionless form of the potential in terms of the variables
p and ¢:
 = J
~ dr{rp2+~lcoS3¢+~p4+up2~~ +'Y[l(~~r + (~:r])· (33.9)
In equation (33.9) we have passed over to the derivative along the z direction
parallel to the body diagonal (111) and neglected the inhomogeneity in the
other directions.
Exploiting the approximation p = const [33], we arrive at the minimization

equation
(33.10)
which is the sine Gordon equation. This standard equation of the theory of
incommensurate structures will be investigated in detail in the next chapter.
Here we restrict our attention to a known solution of this equation in graphic
representation (Fig. 8.33a). According to this solution, the bulk of the crystal
breaks down into fixed-phase regions within which the structure of the w-phase
is described by the wave-vector "'w (see Fig. 8.31). The boundaries between
these regions correspond to the change of the phase, while the structure of
the regions is described by a soliton solution of the sine Gordon equation. In
the equilibrium state the solitons are spaced out at equal distances, forming a
soliton lattice. In Fig. 8.33b the internal structure of domains is represented
only by two periods. Actually, each domain contains many such cells. The same
applies to the intermediate region (shaded area). The wave-vector displacement
8" is determined by the distance between solitons L : 8", = 27r/3L.
Consider now the approximation <p =const in the functional (33.9). The
equation of state
(33.11)
here is similar to equation (32.34) and has a localized solution [21] for
P2 - P1 2 Z - Zo ] -1
P = P2 [1 + P1 cosh -~- , (33.12)
where
1 1 F2
P1,2 = "2(y'r2=F~, ~ = V"2'
This solution may be viewed as the critical nucleus of the phase in the initial
metastable (supercooled) b.c.c. structure. The shape ofthe nucleus is described
by a bell-shaped curve (33.12), thus distinguishing it from nuclei in heterophase
fluctuation theory [21,34].
298 CHAPTER 8
fi
J
~-L --J
--------.-- t
(a)
111111I11111 ~IIIIIIII
1'1~P;P'~~P1~ ~~~~Pl~~ ~~~ ~P,.~
(b)
Fig. 8.33. Structure of the w-phase with", = "'w + {j",: variation of

the phase of the OP ¢ along the body diagonal (a) and the relative
position of the Pl,P2, and P 3 planes (b). The transitional regions
(solitons) from one domain to the other are shaded.
References
1. C.S. Barret, and T.B. Massalski: Structure of Metals, McGraw-Hill (1966).
2. V.A. Somenkov, A.V. Irodova, and S.Sh. Shil'shtein: Fiz. Tverd. Tela 20,
3076 (1978).
3. P. Toledano, and G. Pascoli: Ferroelectrics 25,427 (1980).
4. A.B. Plyusinin, A.N. Dubrovina, and S.M. Finarev: Soviet Phys. Cryst.
24, 344 (1979).
5. A.F. Bol'shakov, A.O. Dmitrienko, and B.V. Abalduev: Izv. Akad. Nauk
SSSR, Neorg. Mater. 15, 1528 (1979).
6. A.G. Kachaturyan: Teoriya Fazovykh Prevraschenii i Struktura Tverdykh
Rastvorov (Transforrnations and Structure of Solid Solutions), Nauka (1974).
7. V.A. Somenkov, and S.Sh. Shil'shtein:Z. Phys. Chern. Neue Folge 117,125
(1979).
8. J .W. Christian: The Theory of Transformations in Metals and Alloys,

Pergamon (1975).
9. M. Cohen, G.B. Olson, and P.C. Clapp: Proc. Internat. Con! on Marten-
site, ICOMAT-79, Cambridge, Mass. (1979) p.l.
10. M. Ahlers: Z. Metallkunde 10,636 (1974).
11. F.A. Kassan-Ogly, V.E. Naish, and I.V. Sagaradze: Fiz. Met. Metalloved.
66, 315 (1988).
12. F.A. Kassan-Ogly, and V.E. Naish: Acta Cryst. B42, 297,306 (1986).
13. Z. Nishiyama: Martensitic Transformation, Academic Press (1978).
14. F.E. Fujita, S. Nasu, and H. Adachi: J. Physique Colloque C4, Supplement
au no. 12, 43, 103.
15. F.E. Fujita: Proc. Internat. Con! on Martensite, ICOMAT-79, Cambridge,
Mass (1979), p.106.
16. R. Oshima, and C.M. Wayman: Scripta Met. 8, 223 (1974).
17. A.L. Roitburd, and G.V. Kurdjumov: Mat. Sci. and Eng. 39, 141 (1979).
18. L.D. Landau, and E.M. Lifschitz: Teoriya Uprugosti (Theory of Elasticity),
Nauka (1987).
19. F. Falk: Acta Metall. 28, 1773 (1980).
20. T. Castan, and A. Planes: Proc. Internat. Con! on Martensite, ICOMAT-
86, Nara, Japan (1986), p.49.
21. V.V. Kondratyev: Fiz. Met. Metalloved. 41, 256 (1976).
22. G.B. Olson: Proc. Internat. Conf. on Martensite, ICOMAT-86, Nara,
Japan (1986), p.25.
23. J.M. Christian: Proc. Internat. Con! on Martensite, ICOMAT-79,
Cambridge, Mass (1979), p.220.
24. N. Nakanishi: Shape Memory Effects in Alloys, Ed. A.J. Perkins, Plenum
Press (1975).
25. T. Saburi, S. Nenna, and C.M. Wayman: Proc. Internat. Con! on Marten-
site, ICOMAT-79, Cambridge, Mass (1979), p.619.
26. C. Teodosiu: Elastic Modes of Crystal Defects, Springer-Verlag (1982).
27. G.K. Barsch, and J.A. Krumhansl: Phys. Rev. Lett. 53,1069 (1984).
28. F. Falk: Z. Phys. B Condens. Matter 51,177 (1983).
29. F. Falk: Z. Phys. B Condens. Matter 54, 159 (1984).
30. L.P. Pitaevskii: Zh. Eksp. Teor. Fiz. 40, 646 (1961).
31. A.E. Jacobs: Phys. Rev. B 31,5984 (1985).
300 CHAPTER 8
32. V.V. Kondratyev, and V.G. Pusin: Fiz. Met. Metalloved. 60,629 (1985).
33. B. Horovitz, J .L. Murray, and J .A. Krumhansl: Phys. Rev. B 13, 3549
(1978) .
34. J.W. Christian: The Theory of Transformations in Metals and Alloys,
Pergamon (1975).
CHAPTER 9
Incommensurate Periodicity Phases
34. General Approach to the Problem
COMMENSURATE AND INCOMMENSURATE PHASES
Thus far we have considered phase transitions that are specified by IR's of space
groups with wave-vectors lying at Brillouin zone symmetric points (Lifschitz
stars). As a result of such transitions, structures arise in the parent crystal; the
periodicity of these structures is strictly commensurate with that of the parent
crystal. Thus, for example, a magnetic ordering over Lifschitz stars gives rise
to magnetic structures with black-and-white (Shubnikov) symmetry lattices
whose periods are multiples of the paramagnetic-crystal Bravais lattice periods
with a multiplicity of 1,2,3, ... (the maximal increase in unit cell volume is by
a factor of 32).
At phase transitions over non-Lifschitz stars the wave-vector modulus may
vary continuously without a change in symmetry, so the period of the structure
that arises at such transitions may be arbitrary with respect to the period of
the initial structure. Formally, these periods may be incommensurate and
therefore phases characterized by non-Lifschitz wave-vectors are said to be
incommensurate (IC). A multitude of such structures, arising at structural
or magnetic phase transitions, are known (Fig. 9.1). Examples are the various
spiral (helical) magnetic structures (SS) or spin wave (SW) type structures.
In vie\v of restricted experimental accuracy in the determination of the wave-
vector, the problem as to the commensurate ness or incommensurateness of
these structures is very difficult to solve on the basis of a purely structural
investigation. It would therefore be more correct at the present stage to talk of
modulated or long-period structures rather than incommensurate structures,
bearing in mind that in practice the wave-vectors of modulated structures differ
little from the wave-vectors "-0 lying at the Brillouin zone symmetric points,
301
302 CHAPTER 9
including the point ""0 = O. Such a structure may be viewed as a long-wave

modulation of some simple commensurate Lifschitz structure. The problem
of the incommensurateness of such structures is an extremely complicated one
and some of its aspects are taken up later in the text. Henceforth (apart
from a special subsection of §36) the term 'incommensurate phase' is used as
a synonym of a modulated structure.
LSW' 1 Six! FflN
Fig. 9.1. Examples of incommensurate magnetic structures.
The thermodynamics of phase transitions inducing modulated structures

displays a number of peculiarities. One of the most remarkable features is the
existence on the phase diagram line of a so-called Lifschitz point, at which
three phases converge at once: the initial, commensurate (C), and incommen-
surate (IC) phases. Other features include the temperature dependence of
the modulated-structure wave-vector and the occurrence of phases with some
'good' (commensurate) wave-vector values. These features arise, to a greater or
lesser extent, from the system's symmetry and are therefore given predominant
treatment in the analysis that follows.
INCOMMENSURATE PERIODICITY PHASES 303
EXPANSION OF A THERMODYNAMIC POTENTIAL WITH CONTINUOUS ORDER

PARAMETERS
The existence of modulated phases signifies that thermodynamic potentials

may have minima that lie not at symmetric (Lifschitz) points of the Brillouin
zone but somewhere in general positions or, more frequently, on symmetric
directions near the Lifschitz point. The motion of the point at which the wave-
vector lies along a chosen direction does not alter the system's symmetry (in
the following this position will be specified more precisely), but the energy
depends on the position of this point, and naturally the wave-vector value that
occurs is such that the energy of the system (the thermodynamic potential)
has a minimum.
Since the symmetry along the chosen direction of the wave-vector q does
not change, the coefficients involved in the expansion of the thermodynamic
potential in powers of the OP should depend on q as a continuous parameter.
With a one-component OP the thermodynamic potential should have the form
(34.1 )
The phase transition occurs when the temperature T = To and the wave-vector
q = "-0 are such that
minA(q) = O. (34.2)
It is convenient to take the origin of the wave-vector to be at the nearest
symmetric point. The quantity A( q) may then be expanded in a power series
of the small vector q. The form of this expansion depends on the symmetry of
the Lifschitz point itself. Two different expansion types may be encountered
for A( q) in the vicinity of the Lifschitz point:
A(q) = r + "(q2 + (3q4, (34.3)
A( q) = r + (1q + "(q2 . (34.4)

To study the minimum of the expression for A( q), it is necessary that the
coefficient of the highest degree of q be positive: {3 > 0 in the case of equation
(34.3) and "( > 0 for equation (34.4). With "( < 0 the expression (34.3) has
a minimum at q = "0 = ±( -"( /2(3)1/2, whereas the expression (34.4) has a
minimum at q = "0 = -(1/2,,( and for any sign of (1. Both situations are
depicted in Fig. 9.2.
In coordinate space the wave-vector q should be referred to the gradient
\7. Therefore the presence in equation (34.1) of a linear term in q means that
304 CHAPTER 9
A(q)
q
o ko o ko
(a) (b)
Fig. 9.2. Behavior of the coefficient A( q) of the quadratic term in the

expansion of the thermodynamic potential near the Lifschitz point of
the Brillouin zone in the absence oflinear invariants in gradients (a)
and in the presence of linear invariants (b).
linear Lifschitz invariants with respect to derivatives exist in the vicinity of a

Brillouin zone symmetric point. The thermodynamics of the phase transition
to a modulated phase in the presence of Lifschitz points will be different from
that in the absence of these points. Both situations are treated in detail in the
next two sections of the book.
Note that in analyzing modulated phases, it is convenient to proceed from
thermodynamic potentials in coordinate space. To derive potentials that are
valuable in the vicinity of some Lifschitz point, the following technique may
be used. At the outset one needs to construct a potential from the OP com-
ponents at the Lifschitz point itself for some IR that describes the main (non-
modulated) structure. Then first-, second-, and higher-order gradient terms
invariant under the initial-phase symmetry group should be added to this ex-
pression. It is these terms that extend the range of applicability of the poten-
tial from the fiducial point to some vicinity of the latter. The group-theoretic
nomenclature of the OP for this vicinity becomes irrelevant since further anal-
ysis of the phases that result by functional minimization is carried over to the
solution of an appropriate differential equation.
35. Phases without Linear Gradient Terms in Free Energy
ONE-COMPONENT ORDER PARAMETER
An overwhelming majority of modulated magnetic structures in crystals arise

owing to modulation of a ferro- or anti-ferromagnetic structure with wave-
vector "'0, the symmetry of which does not allow linear invariants with respect
to the derivatives. Put another way, a modulation-inducing exchange mecha-

nism is at work. In the case of a one-component OP the free-energy functional
should have the form
(35.1 )
with r '" (T - To) and a > O. What corresponds to a minimum of energy

at 'Y > 0 is evidently the homogeneous distribution of the OP (commensurate
phase); for 'Y < 0 the distribution is inhomogeneous (incommensurate phase).
This functional describes an LSW structure.
The energy density ¢(r) depends on the function 1](z) and its two first-
order derivatives, so the equation for seeking the extremals of the functional
(35.1) is found from the condition
(35.2)
In explicit form this equation is a non-linear differential equation of degree

four:
,
L1] + 2U1]3 = 0, (35.3)
where the operator is

(35.4)
It is hardly possible t.o find an exact solution to this equation, so we will

use the asymptotic behavior of a solution near the phase transition point, when
r --> 0 and the OP 1] is small. The zero solution with respect to the parameter
U (coefficient of the non-linear term of the equation) yields 1] '" cos I\,Z. The
non-linear term U1]3 generates odd harmonics, so the solution of equation (35.3)
should be tried in the form of a series:
1] = Al cos I\,Z + A3 cos 31\,z + A5 cos 51\,z + ... , (35.5)
where the amplitudes Ap and the wave-vector I\, should be determined from the
non-equilibrium energy minimum obtained on substituting the solution (35.5)
into the functional (35.1). The calculation of the non-equilibrium energy is a
trivial one and with the help of the simplest integration
IJ
V drcosl\,z = 0 (I\, =P 0), IJ
V drcos 2 K,Z = 2'
1 V1 J 3
drcos 4 I'Cz='8""
(35.6)
306 CHAPTER 9
we arrive at the result
3u 2 2 3u 2
+2(A 1A 3 + A1A5 + A3 A 5) + '2A1A3 + 2(A1A3 A 5 +A1A3A5) + ...
2 2 2 2 U 3 2
(35.7)
Here L(K) is the eigenvalue of the operator L:
(35.8)
Minimizing with respect to the amplitudes A 3 , A 5 , ••• permits all am-

plitudes to be expressed in terms of the amplitude Al of the fundamental
harmonic:
(35.9)
Thus each amplitude is represented by a power series in the parameter uAi ~

(Tc - T); to lowest order Ap ~ Af. We substitute the expressions of A 3 , A 5 , .•.
into equation (35.7) and write the non-equilibrium energy value as a function
of the quantity A 1 :
(35.10)
We now need only to minimize this expression with respect to Al and K. The
best way of minimizing with respect to K is by using the general expression
(35.7), whence we obtain the equation for determining the wave-vector:
(35.11)
where the prime denotes the derivative with respect to the argument. Retaining
only the contribution of the first multiple harmonic, this equation yields
K
2
= 2(
KO
A5)
1 - 24 A2 ' (35.12)
1
where K6 = -1/20:. Minimization of equation (35.10) with respect to Al gives

the equation for the amplitude of the fundamental harmonic:
(35.13)
The quantity L(K), on substituting equation (35.12) into its definition (35.8),
becomes
L(K)=r- ;:[1- (24~~f] =1'- ;: +O(A~). (35.14)
Up to terms At the expressions (35.12) and (35.13) thus yield equations that
give the temperature dependence of the quantities Al and K:
(35.15)
k2 = k2 [1 _ 8(Te - T)2 ] (35.16)

o (T - Te + 64re)2 '
where re = 'Y2/4cx. We transcribe the expression (35.14) as
(35.17)
where Te = Teo + 'Y2/4cx is the temperature of the paramagnetic-incommensur-

ate phase transition.
The equation (35.12) tells us that the modulated-phase wave-vector de-
pends on temperature through the temperature dependence of the amplitude
of the first of the multiple harmonics nearly as AVAr ,. . , At ,. . , (Te - T)2. For
T - Te ::; re the formula (35.16) can be written approximately as
k2 ::::: k2
o
[1 __1 (Te re- T) 2] '
500
(35.18)
whence we see that the temperature-dependent term here is small by virtue of

the smallness of the numerical coefficient; so the variation of the wave-vector
with temperature may be by only a few percent. The contribution of the
consecutive harmonics is determined by higher degrees in Te - T. Therefore
it follows from the result (35.18) that the wave-vector may not go to zero.
Before the expression (3.518) becomes formally equal to zero, the system will
make a phase transition to another state at Te - T ~ re' This state is an
incommensurate phase.
Indeed, the minimization equation (35.3) has a homogeneous solution
l'
T}2 =-- (35.19)
2u
with energy
1'2
e = - - . (35.20)
4u
308 CHAPTER 9
The energy of the incommensurate phase is found from the expression (35.10)
on substituting into the latter the formulas (35.15) and (35.16). In terms of
the quantity l' we find to within (Tc - T)3
~IC = _ (rc - 1')2 (35.21)

6u 27u(r + 63rc)·
The energy equality IC = c determines the first-order phase transition point.
The latter is given by
2 2 2 4 (1 + x)3
-1' = xrc , x = 3(1 + x) + 27 63 _ x .
Thus the incommensurate phase in the (1', /) plane lies in a sector defined by
the two parabolas:
/2
r=-x-. (35.22)
4a
A complete phase diagram, corresponding to the functional (35.1), is presented
in Fig. 9.3. This diagram was first constructed by Michelson [1] in the approx-
imation of one harmonic in the incommensurate phase. Allowance for multiple
harmonics changes the phase boundaries but does not alter the qualitative form
of the diagram [2].
From the diagram, it follows that as the temperature is lowered an incom-
mensurate-to-commensurate phase transition, IC -> C, occurs at / < 0 (ther-
modynamic path a). In many cases, however, an inverse sequence of phases is
observed: C -> IC. This sequence may arise for / > 0 if allowance is made for
the renormalization of / by including into the potential ~ an invariant of the
form -5'1}2(d'l}/dz)2. Instead of /, the potential ~ then involves the effective
parameter
(35.23)
and at a sufficiently large 5 in the condensed phase, where 'I} increases with
decreasing T, the quantity t will decrease with the temperature and if it be-
comes negative, a transition to an IC phase will take place. This will lead to
the following temperature-induced change of the wave-vector in the IC phase:
/\'0 ( t)
= - 2a
1/2
'" (Tc - T)
1/2
. (35.24)
Thus the reverse phase transition sequence C -> IC may possibly be due to
displacement along the thermodynamic path b.
TWO-COMPONENT ORDER PARAMETER
Now consider the functional
e
where "I and are complex conjugate OP components. Minimization of this
e
functional with respect to the components "I and yields the following pair of
complex conjugate equations:
LTJ + 2uTJ 2 e+ nwC- 1 = 0 (35.26)

L + 2ueTJ + nWTJn - 1 = 0
In the absence of an anisotropy these equations have an exact solution:
(35.27)
The anisotropy generates multiple harmonics of the form exp[±i(pn ± 1)], so

the general solution to the system of equations (35.26) should be sought in the
form of a harmonic series:
+ 2: (Apn+1ei(pn+l)"z + A_pn+1e-i(pn-l)"z).
00
"I = A1ei"z (35.28)

p=l
Substituting this series into equations (35.26), we can readily see that the
multiple harmonics have the following smallness with respect to the parameters
u, w, and (Tc - T):
A -pn+l "" w pU p-1Apn-l

1 ,
A pn+l "" w pU PApn+l
1 . (35.29)
In the approximation of two multiple harmonics the non-equilibrium en-

ergy of the IC phase (n ~ 4) is
+ L((n - l)K)A:n+l + L((n + l)K)A~+l +

If> = L(K)Ai
+u(Ai + A: n+1 + A~+1)2 + 2uai(A_n+1 + An+d 2 + 2(n - 1)wA1' (35.30)
On minimizing with respect to the amplitude and the wave-vector, the equlib-
rium values of the harmonics are
_ ( L(K)) 1/2. (35.31)

A1 - --- ,
2u
310 CHAPTER 9
c
o
Fig. 9.3. Phase diagram for a functional (35.1) containing no Lifs-

chitz invariants. The dashed line refers to second-order transitions;
the solid line refers to first-order transitions. a and b are different
thermodynamic paths.
A - _ (n - 1)wA~-1 A _ 2uAiA-n+1 .
-n + -
1 +1 - (35.32)
L({n _ 1),..) + 4uAi' n - L({n + 1),..) + 4uAi'
,..2 ="'6 [1- n{n - 1)2{n - 2)A~r1]. (35.33)
Just as in the one-component OP case, the wave-vector may not go to

zero, for the correction term in equation (35.33) is small. The type of phase
diagram on the (" T) plane remains unchanged (Fig. 9.3).
Thus the wave-vector in systems without Lifschitz invariants depends on
temperature through the dependence of the amplitudes of multiple harmonics
in the distribution of the one- and two-component OP's, the temperature de-
pendent term being insignificant. The transition to a commensurate phase is a
first-order transition with a wave-vector jump. The temperature of this phase
transition is found from the equality of the energies of IC and c. Allowing
for only the first multiple harmonic, the IC-phase energy for the functional
(35.25) is
 _ L2{,..) (n - 1)2{3n - 4)w 2 A2(n-1)
IC - -~ + L{{n _ 1),,) 1 .
The C-phase energy is given by the expression
1'2
c = --
4u
- 21wl (1'
- )n/2 .
-2u
Neglecting the contribution by multiple harmonics to the IC phase, on equating
the expressions for IC and c, we obtain the equation for the transition
temperature:
r
r2=(r-rc)2-4ulwl ( -2u
)n/2 .
So far we have assumed that the inhomogeneity of the structure arises
along one direction in the crystal, that is, the star of the wave-vector k has two
arms (~, -~). Structures for which the wave-vector lies in the symmetry plane
and the star of the wave-vector has more than two arms should be described by
functionals with derivatives relative to several directions. A typica.l functional
with a two-component OP for such situations will be
We explore the modulated phases described by this functional to the one-

harmonic approximation
(35.35)
The corresponding non-equilibrium energy
must be minimized with respect to K x , K y , and AI. The minimization equations

with respect to Kx and Ky have two types of solution:
1: Kx
2
= - 2al'
/
Ky = ° or Kx = 0,
2
Ky
/1
= - 2a1 ;
(35.36)
2 2 /
2:
Kx = Ky = - 2a 1 + 2a2 + a3 '
which are stable under the conditions / < 0, a2 + ~a3 > al and / <
0, a2 + ~a3 < al respectively. The symmetry of both solutions corresponds
to a four-arm wave-vector star, both solutions corresponding to a phase with
inhomogeneity in one direction with ~ = (K, 0, 0) or ~ = (K, K, 0).
THREE-COMPONENT ORDER PARAMETER
We consider one more typical case of a modulated structure described by a

three-component OP ('fll,'fl2,'fl3)' Such a structure may arise, for example, in
a cubic crystal with one magnetic atom per cell, when the OP is represented
by atomic magnetic moment components Mx,My , and !'vIz which transform
312 CHAPTER 9
according to a three-dimensional irreducible representation. We examine the

Ginzburg-Landau functional which corresponds to cubic symmetry and has the
form
<P = tJdr{r L 1]~ ,x

+ u1(E,x1]D 2 + U2 E ,x1]1-
-,E,x1],x({i;, + 0; + 0;)1],x + a1E,x1],x(0; + 0; + 0;)21],x+

+a2 E ,x17,x (0; + oi + 0;)17,x}. (35.37)
The conditions for the functional to be thermodynamically stable,
(35.38)
are found from the following considerations. First, we must require that the
expression (35.37) be positive definite at large values of 1],x. This reduces to
finding positive-definiteness conditions for the higher-order (quartic) form in
terms of energy density:
(35.39)
It suffices to find the conditions under which <P4 takes on positive values at all
the extrema on a circle of constant radius p2 = E,x1]~, since <P4 = p4f, where f
is a function only of the angles determining the spatial position of the vector
'IJ = (1711]21]3).
Thus we need to find the extrema of the functional <P4 - J.tE,x1]~, with J.t
the Lagrange multiplier. The equation
has the following solutions (the value of the extremum for <P is also indicated):
1: <p4(1) = (U1 + U2)p4

1
2: <P4(2) = 2(2u1 + U2)p4
1
31 p 2.,
2 _ 2 _ 2 _ 4
3: 171 - 1]2 - 1]3 - <p4(3) = 3(3u1 + U2)P .
The quartic form is positive definite provided the conditions U1 + U2 >
0, 2U1 + U2 > 0, 3U1 + U2 > 0 are fulfilled simultaneously. The second condi-
tion is automatically satisfied if the first and the third condition are fulfilled;
therefore we obtain two inequalities, U1 + U2 > 0 and 3U1 + U2 > 0, written

out in equation (35.38). The other two inequalities may be obtained from the
analysis outlined below.
For the minimization equation of the functional (35.37) to have a spatially
inhomogeneous solution, it is required that 'Y < 0, just as with one- and two-
component OP's. We investigate the possible modulated phases in the one-
harmonic aproximation:
(35.40)
Like the wave-vector, the modulus and phase of the OP component are found
from the energy minimization condition. On substituting equation (35.40)
into equation (35.37) and integrating, we obtain the expression for the non-
equilibrium energy of the incommensurate phase:
(35.41 )
where
(35.42)
'" being the modulus of the wave-vector", = (x:x, X: y , X: z ). The requirement that
the quartic form in A(",) be positive definite at large x: is fulfilled in exactly the
same way as in the previous analysis and we arrive at the conditions <1'1 +<1'2 > 0
and 3<1'1 + <1'2 > 0 enumerated in the complete list of conditions (35.38) for <1:>.
The expression (35.41) says that the minimization with respect to", is not
associated with that with respect to P>. and ., that is, with the minimization
with respect to directions of magnetic moments.
The equation
(35.43)
has two solutions:
1. (35.44)
2. (35.45)
311 CHAPTER 9
which are stable at 0:2 < 0 and 0:2 > 0 respectively. (It stands to reason that
there exist two more type 1 equivalent solutions with cyclic permutation of
coordinates.) Thus the wave-vector of the structure may lie either along the
cube edge or along the body diagonal of the cube. At an equilibrium value of
/" we have the following values of the coefficient r == ~A("') of the quartic form
in the expression (35.41):
r=~[r- 4(0:;Y:0:2)]' 0:2<0; (35.46)
-
r = '21 [ r - 3,2]
4(30:1 + 0:2) , 0:2
0
> . (35.47)
We now write down the minimization equations with respect to the OP

amplitude and phase
(35.48)
(35.49)
The solutions to these equations determine the following phases:
1p: pi = p2, p~ = p~ = 0,
(35.50)
'J'IC
;0..
= rp 2 + '3(
-
8 Ul + U2 ) P4 .
The phases <POt are not defined. The 1p describes the SW structure with polar-
ization along the cube edge.
2_2_122_
2p: PI - P2 - '2 p , P3 - 0,
sin 2( <PI - <P2) = 0,
whence two cases follow:
1) <PI - <P2 = 1m,

(35.51)
 IC = rp2 + 136 (2U l + U2 )p4.
This solution describes the SW structure with polarization along the cube face
diagonal.
7r
2) <PI - <P2 = 7rn + '2'
(35.52)
IC = rp2 + 312 (7U l + 3U2)p4.
These angles describe the helix in the plane perpendicular to the cube edge.
3p:
The equations to solve for the phases have two solutions:
1) <PI = <P2 = <P3 (modmr),

(35.53)
<1>IC = rp2 + ~(3Ul + U2)p4.
This solution describes the SW structure with polarization along the body
diagonal of the cube.
2) <PI - <P2 = '371" n , <PI -<P3 = '371",

n , <P2 - <P3 = '371""
n ,
(35.54)
<1>[C = rp2 + 1~(5ul + 2U2)p4.
This solution describes the helix in the plane perpendicular to the body diag-
onal of the cube.
u- 1 u=o
2 2 1
2J(2)
k--- Ss ---- U j
U +2..U =0
1 S 2
Fig. 9.4. Phase diagram in the (Ul' U2) plane for the Ginzburg-Landau
functional (35.37). The boundaries of the phases are first-order tran-
sition lines.
316 CHAPTER 9
The other solutions with unequal OP moduli, for example (P1P20) or

(P1P2P3), prove to be unstable for the functional (35.37) with terms of de-
gree not higher than four in the OP. Figure 9.4 presents a phase diagram in
the plane of parameters of the functional (Ul' U2). The boundaries between the
phases have been obtained by equating the energies IC of the phases given by
the expressions (35.50)-(35.54). The phases shown in this diagram are speci-
fied only by the orientation of magnetic moments in SW or SS type modulated
structures. The wave-vector here, as we saw, is not unambiguously related to
the structure, because the terms responsible for this coupling are absent in the
functional (35.37). In terms of cubic symmetry, an energy-density invariant of
the form div 2 TJ is responsible for this coupling. The corresponding contribution
to the energy IC is
V1 J
drw (OTJl
OX + OTJ2
oy + OTJ3)
OZ =
2 1 (~
2"w L:P)..K,).. )2 = 2"wp
1 2 2 2
K, cos"p, (35.55)
where "p is the angle included between the vector." = (TJ1TJ2TJ3) and the wave-
vector "'. Depending on the sign of w, either a state with "p = 0 or a state
with "p = 7r /2 is favorable. In the 1p phase, for example, this will be the
LSW or TSW structure. Thus the coupling of the wave-vector to the magnetic
moment vector in the model (35.37) may be due to the inclusion in of new
inhomogeneous terms of a non-exchange nature.
LIFSCHITZ POINT
With the example of the simplest thermodynamic potential (35.1) with gradi-
ent terms, we saw that as the temperature is lowered a modulated IC phase
specified by the wave-vector "'0 arises from the initial phase at , < 0 , whereas
an ordered homogeneous C phase arises when, > O. In both cases the phase
transition to the ordered phase is a second-order transition.
If the system is subject to external effects X (pressure, field, concentration,
etc.), the quantity r in the potential (35.1) will depend not only on T, but also
on X and the 0 ...... C phase transition will proceed along the r(T, X) = 0 line
in the (T, X) plane. Suppose that the quantity, also depends on T and X and
let us reverse the sign on the ,(T,X) = 0 line. The point (n,XL) at which
both lines intersect is called the Lifschitz point [3]. This point is determined
by solving the two equations:
(35.56)
As we saw, the C phase and the IC phase interchange at , = o. Therefore,

the Lifschitz point is a triple point; that is, three phases (initial, homogeneous,
and modulated) converge at it (Fig. 9.5).
At the Lifschitz point itself, as follows from the equation "5 = -,/20:, the
modulated-structure wave-vector "'0 is equal to zero; the wave-vector increases
monotonically as we withdraw from the Lifschitz point into the interior of the
IC phase. In [1] it is shown also that at the Lifschitz point the tangents to all
the three lines coincide.
Fig. 9.5. Phase diagram in the vicinity of the Lifschitz point L. 0,
initial phase; C, homogeneous phase; IC, modulated phase.
The above features of the phase diagram in the vicinity of the Lifschitz
point, which have been derived from an analysis of a system with a one-
component OP, are general. With a two-component OP, only the shape of
the lines themselves changes, while the topological structure of the phase dia-
gram remains the same as before.
Note that the homogeneous phase 1 is not necessarily a ferromagnetic
phase. The thermodynamic potential (35.1) (or (35.25)) describes a phase tran-
sition to a state with a wave-vector near some symmetric (Lifschitz) point and
we deal with a modulation of the corresponding Lifschitz structure. If the sym-
metric point lies at the center of the Brillouin zone, then the modulated struc-
ture is a ferromagnetic one; otherwise the structure is an anti-ferromagnetic
one.
We conclude by noting that [4,5] point out the existence of Lifschitz points
due to gradient invariants of degree three made up of quantities of the form
(35.57)
For an experimental realization of the Lifschitz point, see [7].

318 CHAPTER 9
36. Phases with Linear Gradient Terms
THE SOLITON LATTICE
Consider a two-component (1], e) OP system that is described by the Ginzburg-

Landau functional
(36.1 )
with the conditions u > 0 and 'Y > 0 ensuring that the extremals of the func-
tional are stable. The signs of wand (J' may be arbitrary. We have immediately
assumed that the structure is homogeneous in the x and y directions, so the
volume integral reduces to a one-dimensional integral, L being the size of the
crystal in the z direction.
The potential can be minimized with the aid of the methods used in the
previous section, where the solution is tried in the form of a harmonic series
and the amplitude of the harmonics and the wave-vector are found from the
condition that be minimum. This procedure, however, is valid not far from
the phase transition point. If we wished to go deeper into the condensed-phase
region, we would have to allow for a large number of harmonics. Another
approach can be used in which one has to introduce a certain simplification
into the functional (36.1) and to obtain a minimization equation with a known
exact solution. This program dates back to Dzyaloshinsky [7] who suggested
using the OP constant modulus approximation
p = const, (36.2)
e
where p is defined by the equations 1] = peicf> and = pe-icf>. In this approxi-
mation the functional (36.1) depends only on the distribution of one quantity,
namely, the phase
(36.3)
and depends on the modulus of p as a parameter.

The variation of leads to the following equation for the phase:
d 2 (n¢) .
~ + vsm(n¢) = 0, (36.4)
INCOMl\1ENSURATE PERIODICITY PHASES 319
where v is the effective anisotropy parameter:
(36.5)
In the absence of anisotropy, equation (36.4) has the solution ¢ = liZ, which de-
scribes a one-harmonic incommensurate structure, for example, a simple helix.
On the other hand, equation (36.4) has also a homogeneous solution, which cor-
responds to an incommensurate structure. At finite v, equation (36.4) should
describe an inhomogeneous OP distribution. We can readily find one exact
periodic solution to this equation.
To begin with, we obtain the first integral of the equation by integrating
the left-hand and right-hand sides with respect to d¢:
~(ds;)r -vcosn¢ = f,
c being the integration constant. The resulting equation may be solved ill
quadratures:
vv r"'/2 dB
(36.6)
-;-z = Jo Jl _ re2 sin 2 B'
where re is some constant that is expressed in terms of the integration constant

c and the parameter v. The equation (36.6) expresses ¢ as an elliptic function
of the amplitude am (u, re):
2
¢(z) = ~am (vv )
-;-z, re , (36.7)
where re is the modulus of the elliptic function (0 :::; re :::; 1). The quantity x
must be found from the energy minimum of the system; the second integration
constant, that is, the initial coordinate z, is set equal to zero.
The energy of the state in which the OP distribution is described by the
formula (36.7) is expressed in terms of the complete elliptic first- and second-
order integrals J( and E:
<{lIe = rp
2
+ up 4 - 2p
2 ¢VV + 2p 212
IO"I-}, V (re - 2 2 4E)
- - 2 - +}"? 2 . (36.8)
nre \. n re re~
Minimization of this expression with respect to re leads to the equation
(36.9)
320 CHAPTER 9
p
~=f
311
L
-n~~~T------- __
Fig. 9.6. Amplitude function am(z,re) for different values of the

parameter reo
which enables re to be found for a given anisotropy parameter v.

The variation of re between 0 and 1 corresponds to the variation of v from 0
to Vc. For such variation, the form of the amplitude function changes radically.
Inspection of Figure 9.6 shows that a periodic structure arises which has some
period L and evolves with varying parameter v. With v approaching vc , a
segment arises on the length of the period. On this segment the phase is nearly
constant, but it changes drastically at the ends of the period, where the phase
variation occurs at 27r /n. When v --t Vc the fraction of the constant-phase
segment increases. Under these conditions the system may be represented as
a periodic structure of commensurate-phase domains (with a constant ¢> value
that is a multiple of 27r /n) separated by domain walls, that is, solitons. The
period of the function (36.7) is
(36.10)
The soliton picture described above is easy to see if we make use of the
asymptotes of complete elliptic integrals. The soliton lattice period diverges
logarithmically as v --t Vc (that is, as re --t 1):
4re 4
L= r.7ln~. (36.11)
Vv 1 - re 2
Since the modulation wave-vector K, ' " 1/ L, it is clear that for v --t Vc the wave-
vector tends to zero. That is to say, the wave-vector of the incommensurate
phase tends to its commensurate value "'0'
We wish to illustrate the evolution of the spatial distribution of the OP
described by the solution (36.7), with an example of a modulated SS structure.
Let the wave-vector of the helix be directed along the principal crystal axis (z
axis) and let the magnetic moments lie in the basal plane (x, y). The magnetic
anisotropy in this plane is described by an invariant of the form M+ + M:!..
The nth-order anisotropy singles out n equivalent directions in the basal plane,
the atomic magnetic moments tending to adjust themselves to these equivalent
directions. If there is no anisotropy, the magnetic moments rotate uniformly
during displacement from layer to layer in the z direction. If the anisotropy is
infinitely large, the magnetic moments approach one ofthe n specific directions.
In keeping with the solution described by the function am ({i z, re) (Fig. 9.6),
the orientation of atomic magnetic moments at v values sufficiently close to
Vc (that is, when sufficiently removed in temperature from the point Tc) is
shown in Figure 9.7. There are seen to arise stacks of ferromagnetic planes
whose magnetic moments are successively aligned with the anisotropy axes.
The transition between two stacks occurs over a small length compared to L
and corresponds to a soliton. For v = Vc there is only one commensurate-phase
domain of infinite length.
Fig. 9.7. Spiral structure in the presence of an anisotropy in the basal plane.
We perform a harmonic analysis of the solution corresponding to the soli-

ton lattice. Exploring the Fourier expansion of the function am (u, re), we write
down the series
2
= KZ + E ( 'irK') sin(pnKz),
00
¢(z) (36.12)
p=l n cosh P""'j(
by virtue of the expression (36.7), where
K=--
7rVv (36.13)
nreI<
322 CHAPTER 9
is the wave-vector of the structure. Thus, in full accord with the results of §35,
where a two-component OP system without a Lifschitz invariant was consid-
ered, extra harmonics e i (n±l)I<z and multiple counterparts arise alongside the
fundamental harmonics eil<z when an anisotropy is present in the basal plane.
i 1----___
oI--------~------~~
o,~ i
x~
o os i
Fig. 9.S. Variation of the wave-vector with the reduced-anisotropy

parameter v.
The wave-vector (36.13) depends on temperature through the dependence

of the quantity v on the OP modulus: p'" (Tc -T)1/2. As follows from equation
°
(36.9), the limit v -+ corresponds to re -+ 0. Expressing re in the formula
(36.13) by means of equation (36.9) and using the asymptote of the quantities
J{ -+ 7r /2 and E -+ 7r /2 with re -+ 0, equation (36.13) yields the value of the
wave-vector of the structure
10- 1
11:0= - (36.14)
'Y
at the instant it emerges from the paraphase. The wave-vector versus tem-
perature curve, determined by the expression (36.13), is shown in Fig. 9.S in
terms of the dependence of the elliptic modulus re on the reduced-anisotropy
parameter v. This behavior conjointly with the expansion (36.12) determines
also the evolution of the harmonics in the Fourier expansion of the OP. Figure
9.9 demonstrates a continuous transition from an incommensurate 55 (simple
spiral) structure to a commensurate (ferromagnetic) structure as the applied

magnetic field is varied from 0 to the critical value He determined by equation
(36.9) for n = 1.
_l~_L_
J __
---.-1-------- ;r' = 1
Fig. 9.9. Evolution of the Fourier representation of the soliton lattice

to the commensurate phase. The picture is constructed for the first-
order anisotropy (n = 1) and refers to the magnetic field applied
perpendicular to the wave-vector of the SS structure.
SOLITON LATTICE STABILITY
Next we need to establish the range of variation for the parameter of the func-
tional (36.3) over which the solution (36.7) of the minimization equation is
stable. The solution of interest arises from the condition that the first varia-
tion of the functional be equal to zero: 6<1> = O. The stability of the solution
determines the sign of the second variation: 02<1> > O. We write out the expres-
sion for the second variation in the form [8]:
(36.15)
324 CHAPTER 9
where
~ ( d
D</></> = 'Yp2 dz
)2 - Wpn cos n¢, (36.17)
D~ p</> = 2(1P dz
d d¢ d 2 n 1 .
+ 2'YP dz dz - wn P - sm n¢. (36.18)
In the expression (36.17) we have used the symbolic notation (djdz)2, which
implies
We start by exploring the initial phase characterized by a zero OP value,

P = O. The stability of this phase is determined by the quantity D pp , which
may be written as
1
-D
2 H
=
(12
r - -
'Y
+ -L1 J (d¢
dz'Y -
~
+ -(1)2
'Y
> O. (36.19)
Hence it follows that for

(12
r= - (36.20)
'Y
the initial phase becomes unstable with respect to the formation of a structure
with an inhomogeneous OP phase that satisfies the equation
(36.21)
We now investigate the stability of an incommensurate phase with P "I

O. The stability is determined by the three coefficients (36.16)-(36.18) of the
quadratic form (36.15). First we deal with the term that contains D</></> in 82 <1>.
Along with 8¢ phase variations limited at Izl -+ 00, we should consider also
variations proportional to z at large z. Therefore non-zero terms may appear
outside the integral when performing integration by parts in the interval with
D</></>. To ascertain the role of these terms, we represent the arbitrary variation
of 8¢ as [8]:
8¢ = o:"po + 8¢' , (36.22)
where "po is a function with a 'poor' asymptote at z -+ ±oo, and 8¢' is bounded
within these limits. The contribution to 82 <1>, with which we are concerned,
breaks down into three parts:
Consider now the eigenfunctions of the operator - fi.r - v cos <jJ. The corre-
sponding eigenvalue equation
(36.24)
is a Lame equation [9] with a numerical parameter I = 1. This is easy to

verify if we exploit the relation sin am( u, re) = sn u from the theory of elliptic
functions. The equation (36.24) then assumes the standard form of the Lame
equation:
(36.25)
where
Fv re 2 _
u= - z, {= - {,
re v
(The general form of the Lame equation with integral indices is obtainable from
equation (36.25) by replacing the coefficient of re 2 sn 2 u : 2 ~ l(l + 1).)
It is known that the minimal eigenvalue for equation (36.24) is { = 0;
to this eigenvalue corresponds the function 1/J = dn u. There is also another
solution to the equation for the same eigenvalue:
1/Jo = dn u l
tio
ti du
-2-'
dn u
(36.26)
but it belongs to another class of functions since it has a 'poor' asymptote at

large u : 1/Jo "-' u. It is this solution that should be identified with the quantity
'1/'0 involved in equation (36.22), so the last term of the expression (36.23) goes
to zero.
Using the expressions (36.7) and (36.26), we can readily obtain the identity
o<jJ = _2.. 1/Jo (Fv z) (36.27)

are nre re
to evaluate the variation of the functional due to the phase variation o<jJ =
a\Il o . For small a we may write
o<jJ
<jJ + a1/Jo = <jJ - ~anre are ~ <jJ( re + ore), (36.28)
326 CHAPTER 9
where Ore = - ~anre describes an equivalent variation of the parameter reo We

see that the variation of the functional due to the variation o</> = mpo reduces
to the second variation with respect to the parameter re:
(36.29)
This expression should replace the second term on the right-hand side of the
expression (36.23), which now may be represented as
1
2L J A 1
dzD¢¢(O</»2 = 'Yp2I J dzo</>' (-d
2
dz 2 - v cos</>)
2<1>Ic
o</>' + 2"1 aare 2 (ore)~.
?
(36.30)
Similarly, we calculate the contribution to P by the mixed variation
1
2L
J 2 n - 2 1
dzDp¢o¢>Op = -2'Yp v-n-I
A J. dz Sll1 </>o</>' + a 2 <1>IC
apore opore. (36.31 )
Thus we have arrived at the result that the variation of a functional with
a linear asymptote with respect to z is equivalent to the variation of with
respect to the parameter reo The derivatives a 2<1>IC/are 2 and a 2<1>IC/areap can
be calculated using the explicit expression (36.8) for the incommensurate-phase
energy:
a 2 <1>IC = 4v 'Yp2 1 E (36.32)
are 2 n 2 re 4 (1 - re 2 ) J{'
a<l>IC 4 n - 2 E2 - J{2(1 - re 2 )
- - = - V'YP--
2
(36.33)
areap n re 3 J{2(1 - re 2 ) .
The problem then arises of diagonalizing the quadratic form with respect
to o</>' and op. This problem is solved by the linear substitution o</>' = o¢+ fOp
and the requirement that the function f obey the inhomogeneous differential
equation
d2
( dz ) n- 2
2 + v cos</> f + -;:;pvsin</> = 0,
which, on explicitly using the expression (36.7) for </>, reduces to
(36.34)
The general solution of this equation,
f = --dn
n - 2 u ( u + Cl + C2
np
1 0
u
-du
2 -) '
dn u
(36.35)
has the requisite periodicity f(u + 2/C) = f(u) and the required periodicity of
the functions snx and cnx if we choose C2 = -l{(1- re 2)/E.
On calculating all the integrals, the completely diagonalized quadratic
form (36.15) for the incommensurate phase is
021> = Dpp(Op)2 + Drere(Ore)2 + 2ip2± J dzoJ( - d~2 - V cos</> )oJ, (36.36)
2 7r 2 0"2 E - (1 - re 2)l{ 7r 2 0"2 E2 - (1 _ re 2)l{2

Dpp=4up +Sn(n-2)-:y E2l{ -16(n-2)-:y El{3(1-re 2) ,
(36.37)
(36.38)
The new variable Ore results from the diagonalization of the integral-free terms
(36.30) and (36.31) and is related to Ore by the equation
_ n - 2 E2 - l{2(1 - re 2 ) op
Ore = Ore - -2- El{ -p .
For the phase to be stable, all the coefficients of the quadratic form (36.36)
must be positive. We first transform the integral term in equation (36.36) by
expanding oJ in Lame equation eigenfunctions:
OJ = J dlo:(l)1jJ(l).
Then
(36.39)
since min l = 0 for equation (36.24). Therefore, the state of the soliton lattice
is stable relative to the phase fluctuations oJ. Also
Drere > O. (36.40)
We explore the stability boundary Dpp o for fluctuations of the OP

modulus. Near the paramagnetic phase (re -+ 0) E -+ l{ -+ ~ and, as follows
from the expression (36.37), the stability boundary Dpp = 0 passes along the
p2 = 0 line and thus coincides with the stability boundary (36.20) of the initial
phase. So the phase transition from the paramagnetic phase is a second-order
transition.
Using the asymptote of the functions E and l{, the equation Dpp = 0 for
re -+ 1 yields the second stability boundary
12 3 4 7r 2 2 0" 2
re In re' = 32(n-2) (-r),' (36.41 )
328 CHAPTER 9
where re' = VI - re 2 ; the quantity re 2 satisfying equation (36.9) is here ex-

pressed by the equation
(36.42)
As is seen from equation (36.41), the stability of the soliton lattice with
respect to the variation of the amplitude p is perturbed at values of re less
than unity (but in a logarithmically close vicinity of unity). This means that a
continuous transition to a commensurate phase cannot be realized for re = 1.
By comparing the energies of the incommensurate and commensurate phases,
it may be shown that a first-order transition between these phases occurs at
re' ~ 1. The quantity re' is determined by the equation [8]:
(36.43)
THE DEVIL'S STAIRCASE
The IC-C phase transition, which is described by the soliton mechanism, oc-
curs owing to the competition of two terms in the thermodynamic potential
(36.3). One of them, containing a phase gradient, tends to bring about an
inhomogeneous OP distribution in the system, that is, a modulation with the
wave-vector KO. The other term, allowing for the anisotropic energy, tends to
make a homogeneous structure with the phase ¢, which is determinable from
the relation cos n¢ = ±1, where the sign is chosen depending on the sign of the
parameter v.
We have assumed that the starting thermodynamic potential (36.1) or its
simplified expression (36.3) describes a phase transition with a wave-vector
near some Lifschitz point of the Brillouin zone. We call a phase with a wave-
vector at such a point a homogeneous phase. If we consider the behavior of
our system as the temperature is varied, we can see that when T < Tm a
modulated structure arises which has a wave-vector KO' As the temperature is
elevated the KO decreases gradually and, as a result, a homogeneous structure
arises of which the period is commensurate with the initial-phase period since
it is determined by a Brillouin-zone Lifschitz point. Therefore, a homogeneous
phase is a commensurate phase in the aforementioned sense and an inhomo-
geneous phase is, generally speaking, incommensurate. The chief result of the
previous subsection is that the commensurate phase is stable in some region of
the parameter KO.
Dzyaloshinsky was the first to adduce arguments supporting the idea that
variations of the wave-vector with temperature should occur not smoothly but
as discontinuous jumps between individual commensurate values in which the
corresponding phase is stable. Such stepwise variation of the wave-vector came
subsequently to be called the devil's staircase [10].
We have seen what role the anisotropic Dzyaloshinsky invariant cos n¢J
plays in transitions between IC and C Lifschitz phases. The integer n is a
characteristic of a two-dimensional IR at a Lifschitz point, and for all the four-
teen Bravais lattices it may be equal only to 3,4,6,8,12 (§14). Let us consider
some non-Lifschitz point that lies on a symmetric direction, say Ii, = flhl,
where 0 < fl < ~. In a crystal with a finite number N of cells, closed ac-
cording to the Born-Karman condition, the wave-vector runs over the values
IC = (lIN)(27rla), where 0 < I < N - 1; thus the parameter fl runs over ra-
tional values min only. Thus we take the wave-vector Ii, = flh 1 with the only
component
27rm
IC = - - (m < n) (36.44)
na
(this vector correpsonds to a point in common on the flh 1 line) and consider the
corresponding two-dimensional IR of the parent-crystal space group G" (the IR
is realized on the arms Ii, and -Ii,).
It is normally assumed that the wave-vector symmetry does not change on
the line and that the group G" is the same for all fl. This is really the case if
we consider the wave-vector group poil'lt symmetry alone. But the translation
subgroup will be different as a function of the number fl = min. The trans-
lation subgroup contains minimal translations by the quantity na. The basis
functions of the IR on the arms Ii, and - I i , vary with varying translation vector
tn according to the law: W" '" exp( i/d) and '1/J-" '" exp( -ili,t). The quantities
('1/J,,)n and ('1/J_,,)n are invariants under translations for the wave-vector (36.44),
so the invariants should consist of powers of the OP's 'T}n and ~n. vVhatever
the rotation group G", only two invariants may be set up from these powers:
(36.45)
In form, these invariants are the same as those existing for two-dimensional
representations at Lifschitz points; however, the number n may be arbitrary
for non-Lifschitz points. The difference between these invariants lies in the
circumstance that the number n characterizes the I group (c n or cnv ) rotation
axis for Lifschitz points and minimal translations for non-Lifschitz points.
330 CHAPTER 9
In moving along the line in the Brillouin zone, the quantity n varies from
point to point according to the wave-vector (36.44). Alongside the variation
of n, there is a change in the translational symmetry of the group G" and in
the energy invariants. The latter circumstance makes the energies of phases
with close wave-vector values different, thereby ensuring the energetic favor-
ableness of certain wave-vectors. It is on the strength of these considerations
that Dzyaloshinsky arrived at the conclusion that the wave-vector may vary
stepwise between sequential rational values with varying temperature [11].
All the arguments concerning the stability of phases with a Lifschitz wave-
vector may be applied to a phase with a non-Lifschitz but commensurate vector.
With varying KO the modulation wave-vector will abruptly pass to a value that
corresponds to a commensurate phase with some value of min and this phase
will be stable over a certain interval of functional parameters, then there will be
a jump to a sequential rational min value, etc. In each cascade of these phase
transitions certain values of min occur that are dependent on the parameters
of the thermodynamic potential.
VVithin the framework of the mean-field approximation for an Ising mag-
net with positive values of exchange integrals for nearest neighbors and with
negative values for next nearest neighbors, Bak [12] constructed, with the help
of a computer, phase diagrams on the temperature-exchange integral plane
(Fig. 9.10). It has turned out that a large number of modulated phases ex-
ist. These are characterized by the values nlm = i, i, i, ... , /7 and each of
them has an individual region of existence. If we vary the temperature (with
the exchange integral being fixed), we will obtain a sequence of phases with
some of these nlm values. This is a model example of the devil's staircase. A
variety of systems exist for which the devil's staircase (that is, a discontinuous
wave-vector variation) has been observed experimentally [13-17].
A number of physical factors should destroy the devil's staircase, espe-
cially at large values of n. Here belong primarily cooperative motions in the
soliton lattice, which describes the structure of the incommensurate phase near
the boundary of its stability. Domain boundaries, described by solitons, are
infinite planes perpendicular to the wave-vector. Elementary excitations of
such boundaries are phasons, that is, flexural waves that propagate in the
plane of the boundaries, and also oscillations of the boundaries themselves rel-
ative to one another. Allowance for these excitations leads to shifting of the
commensurate-phase stability boundaries. Phasons narrow the stability range
of the incommensurate phase [12].
INCOMl'vIENSURATE PERIODICITY PHASES 331
Fig. 9.10. Phase diagram for ANNNI model [12]. .:71 > 0 is the
exchange integral between nearest neighbors in the direction of the
modulation; .:72 < 0 is the exchange integral between next nearest
neighbors.
A more substantial influence is exerted by quantum fluctuations, that is,

soliton lattice zero-point vibrations. At sufficiently small n, a transition to
an appropriate commensurate phase is possible owing to these vibrations. The
other steps of the devil's staircase will be smeared out by quantum fluctuations.
STOCHASTIC REGIME
Recently it has been found that the physical models described by an energy
functional of the type (36.3) (before proceeding to a continual limit in which
the lattice parameter tends to zero) exhibit peculiar behavior near the IC-C
phase transition boundary. Along with the commensurate and incommensurate
structures, some chaotic structures with random distances between solitons
(describing in the incommensurate phase the wall between the domains of the
commensurate phase) may exist in these models. This was first disclosed by
Aubry (see his review lecture [18]) in the Frenkel-Kontorowa model [19,20]
for an atomic array in a periodic potential, in [21] in the three-dimensional
anisotropic Ising model allowing for the interaction with next nearest neighbors
(the so-called ANNNI model), in the discrete </;4 model [22,23], and in the
discrete Peierls model [24,25].
332 CHAPTER 9
An analysis of the solution of the energy minimization equation in the

('coordinate'-'momentum') phase plane has shown that at large values of the
anisotropic potential (for example the quantity v in the functional (36.3))
stochastic paths (trajectories) corresponding to random structures arise along
with the usual smooth trajectories corresponding to incommensurate struc-
tures. Such a structure may be pictured as consisting of fragments of com-
mensurate structures with different periods; this should lead to smearing of
the corresponding Bragg peaks in the diffraction pattern. The mean period
with respect to the entire random ensemble may be incommensurate with the
parent-crystal period. Thus the wave-vector of the superstructure in the afore-
cited systems may vary not only, say, between commensurate values (the devil's
staircase), but also stochastically. By contrast with incommensurate phases de-
scribed by an unfixed soliton lattice, a chaotic phase corresponds to solitons
fixed on the host crystal lattice. An activation energy is needed to shift the
chaotic soliton lattice; in this respect the chaotic structure is closer to the
commensurate structure although its mean period in the general case is incom-
mensurate with the host lattice period. In contradistinction to commensurate
phases engendering a devil's staircase, chaotic phases are metastable.
37. Multi-N.-structures
CONDITIONS FOR MANY-ARM STRUCTURES TO BE THERMODYNAMICALLY

FAVORABLE
Up to this point we have studied modulated structures exhibiting inhomo-

geneity with respect to one direction, which is specified by one modulation
wave-vector "'. At the same time, this vector may also belong to a many-arm
star whose arms correspond to equivalent directions in the crystal. In the gen-
eral case the spin density of the crystal should be a superposition of all arm
contributions. When all the arm contributions, except one, are equal to zero,
one talks of a 1", structure; if at least two arm contributions are non-zero, the
corresponding structure is called a multi-N.-structure.
We have already stated that in a neutron diffraction investigation the
spatial modulation of the initial commensurate phase is always assumed to go
along one direction in a single-domain sample. Exceptions are apparently two
materials, CeA1 2 and Nd, in which multi-",-structures are assumed to exist. To
resolve the dilemma as to what kind of structure occurs (IN.-structure or multi-
N.-structure), attempts are made to detect experimentally fine concomitant
properties of these materials, properties that would be different m crystals

with different arm contributions. This subject has been widely disputed (see
the book [26] and [27-29]), but the discussion has not yet led to an unambiguous
solution of the problem. We will try to understand, proceeding from an analysis
of the simplest Ginzburg-Landau functional allowing for the inhomogeneity
of the OP in two directions, what causes make the occurrence of multi-~
structures a rare phenomenon.
Thus we consider the following form of the Ginzburg-Landau functional
for a one-component OP [30]:
(37.1)
with u > O. For the spatially inhomogeneous OP distribution to be favorable,

it is necessary that 'Y < 0; for the increase of inhomogeneities to be restricted,
it is required that a > 0 and a + a1 > o.
As a trial function of the variational problem, we take
'1](1') = '1]1 cos K.1 r + '1]2 cos ~2r, (37.2)
where the amplitudes '1]1, '1]2 and the wave-vectors ~1, ~2 are found from the
condition that the potential be minimal, ~1 and ~2 lying in the (x, y) plane.
The problem reduces to one of minimizing the form
(37.3)
"1 and "2 being the moduli of the vectors ~1 and ~2.
The term -a1 allows the wave-vectors to be referred to the crystal axes;
a favorable position of the vectors at a1 > 0 is along the bisectors of the x and
y directions, for a1 < 0 the favorable position is along x or y. Assume, for
definiteness, that a1 > 0, so that for the minimum (37.3) we have "rx "'r
= y
and "~x = "~y, where the term proportional to a1, involved in the expression
(37.3), cancels out. Minimizing with respect to the moduli of "1 and "2, we
determine the values of these vectors:
(37.4)
334 CHAPTER 9
As a result, the expression for non-equilibrium energy (37.3) reduces to a quar-

tic form in the amplitudes "11 and "12:
(37.5)
The resulting form is isomorphic to the energy functional for a homoge-

neous two-component OP and the conditions for the corresponding phases to be
stable are known (see, for example, §17). If we label the coefficient of ("1f + "1D2
°
by U1 and that of "1f"1~ by U2, then the phase "1f =1= 0, "1~ = is stable in the
° °
general case, if U1 > 0, U2 > and for U1 > 0, U2 < the phase "1f = "1~ =1= °
is stable. In the case (37.5) both coefficients of the quartic terms are positive,
therefore a stable solution is one with either "12 =°or "11 =
0, that is, the state
°
with 1~ structure.
To make the multi-~-structure energetically favorable ("11 =1= and "12 =1= 0),
it is therefore necessary to make the coefficient of "1f"1~ in the effective potential
(37.5) negative. This can be achieved only by including extra terms into the
functional (37.1), terms that would be of order "14. These should inevitably
involve spatial derivatives of "1. For example, the presence in the energy of an
invariant of type W"12( {)2"11 ()x{)y) 2 changes the coefficient of 17f"1~ by an amount
'" wKiK~. If this quantity is of the order of u, the overall coefficient of 17i17~
is likely to reverse sign at an appropriate value of w. In this case the multi-
~-structure will be favorable. However, since the wave-vectors of modulated
structures are normally small, this situation is difficult to realize.

In the following we will construct a Ginzburg-Landau functional for CeAh
with allowance for all invariants of degree four in the OP and see that, indeed,
this functional contains terms that allow, in principle, the energetic favorable-
ness of the multi-~-structure.
MULTI-~-STRUCTURE IN CeA12
Neutron diffraction studies of CeAh reveal a set of three magnetic satellites

around each equivalent point of the reciprocal space ~o = (~ ~ ~). The satel-
lites correspond to modulation wave-vectors
(37.6)
with a small value of the parameter p,. Thus the wave-vector star in the struc-
ture is a 24-arm star. A 3~-structure is assumed to occur in each domain
corresponding to the wave-vectors (37.6) which group around the point ~o.
The commensurate magnetic structure in CeAl 2 is described by the one-

dimensional IR T2 of the star {~o} (crystal space group Ok). The Ginzburg-
Landau functional for the representation T2{~O} has the form [30]
 = ~ Jdr{ 117 2 + U1]4 + (-y + a17 2)( 1]; + 1]; + 17;) + (r1 + a11]2)( 1]x + 1]y + 1]z )2+
+(a + )..1]2)(1]xx + 1]yy + 1]zz)2+
+( a1 + )..1772)( 1];x + 1];y + 1];z - 21];y - 277;. - 21];z)+
+(a2 + )..21]2)1]xy.(1]x + 77y + 1].)+
+(a3 + )..31]2)(1]xxx + 1]yyy + 1]zzz)(1]x + 1]y + 1]z)}, (37.7)
where the atomic spins are related to the OP as follows:
s(r) = 1]exp(i~or)(111).
'Ve ascertain the conditions under which a 3",-structure of the form
(37.8)
exists; the vectors "'1, "'2, and "'3 are determined by the empirical relations
(37.6). On substituting equation (37.8) into the functional (37.7) and carrying
out the integration, we obtain the expression for non-equilibrium energy in a
form isomorphic to a homogeneous phase with a three-component OP:
(37.9)
where u = U + aK,2/2 + )..J.;4. In deriving this expression, a minimization with

respect to the value of the wave-vectors was carried out yielding
r (37.10)
-2a·
The stability of the phase specified by 1]f = 1]~ = 1]5 ::P requires that °
the coefficient of the term (1]r + 1]~ + 1]5)2 be positive and the coefficient of
(1Jf1]~ + 1]f1]5 + 1J~1]5) negative (see §18). Thus the following inequalities should
be fulfilled for the 3", structure to be favorable:
(37.11)
336 CHAPTER 9
so that the functional (37.7) invariant proportional to A1 plays a decisive role.

Taking into account the smallness of the wave-vector "', we come to the conclu-
sion that an anomalously large value of the parameter A1 and an anomalously
small value of the parameter u are required for the 3", structure to occur in
CeAI 2 . The smallness of u implies that the system should be in the vicinity
of the tricritical point, and it may be thought that applying external effects
(pressure, alloying) would lead to a first-order phase transition. It would be
interesting to check this experimentally.
MULTI-",-STRUCTURE IN Nd
The experimental situation in the case of Nd is much richer than that for
CeAh (Fig. 9.11) [32]. Nd pertains to a group of rare-earth metals having
an h.c.p. structure in which the atoms occupy the positions 2(c) and 2(a) of
the group D~h (Fig. 9.11). At TNl = 19.9 K there arises on position 2(c)
atoms a longitudinal spin-wave structure with modulation wave-vectors ±"'1 =
J-lb 1 , ±~2 = J-lb 2 , ~3 = J-l(b 2 -bt). These correspond to six satellites that lie in
the basal plane near each crystal reciprocal-lattice site. As the temperature is
lowered down to TN2 = 19.3 K a second transition occurs which is characterized
by a small deviation of the magnetic moments and modulation wave-vectors
from the symmetric directions in the basal plane. On the neutron diffraction
patterns this is manifest in the splitting of magnetic satellites. In the following
we restrict our attention to the temperature range 7.5 K< T < 19.9 K in which
a third phase transition comes about at TN3 = 7.5 K.
In the past few years three versions of magnetic structure have been pro-
posed to decipher neutron diffraction patterns of Nd. It was originally assumed
[32] that a 3",-structure (with wave-vectors "'1, ... ''''6) takes place in this case
which is accompanied by distortions of a lattice of the same periodicity. How-
ever, an ad hoc experiment refuted this assumption [33]. Then a 1",-structure
model was suggested [34] in which the large number of magnetic satellites in
the structure is attributed to the presence of domains. This model, however,
does not account for certain temperature dependences that are observed exper-
imentally; this applies, in particular, to the temperature behavior of satellite
splitting. Finally, the third model [35] presupposes a participation of two arms,
~1 and "'2, in magnetic structure (2",-structure) formation. As shown in [36],
the presence of an inhomogeneous anisotropy in this case leads necessarily to
the vectors ~i deviating from the symmetric directions. Thus the latter model
offers the most organic explanation of the effects observed in Nd.
1(,,)
2ie)
l[a)
.lie)
21")
Fig. 9.11. Magnetic structure of neodymium in two temperature in-

tervals: 7.5 < T < 19K (a) and T < 4.5K (b).
We analyze the conditions for multi-K-structures to be thermodynamically

favorable in Nd. By the standard group-theoretic procedure, it is readily ver-
ified that the OP of interest contains two components (1]~) and transforms
according to the two-dimensional IR 712 of the point r (KQ = 0) of the space
group Dth' The Ginzburg-Landau functional for this case should have the
form [30]
withx± = x ± iy being circular cylindrical coordinates. Here the OP compo-

nents 1] and ~ (1] = C) and the magnetic moment density are related by the
equation
M = 1]m + ~m·, m = (1, -i, 0). (37.13)
In the expression for q, the invariant series
(37.14)
338 CHAPTER 9
prove irrelevant in investigating the stability of multi-",-structures and are

therefore deliberately omitted.
We try a solution, minimizing the functional (37.12), in the form
The real amplitudes "1i determine the magnitude of the corresponding arm
contribution, the <Pi are the angles between the directions of the magnetic arm
contribution and the axis h. We express the wave-vectors "'i in terms of the
polar coordinate system, where the angles 1/;; too are referred to the h1 axis:
"'1 = ",(cos 1/;1, sin 1/;1, 0), "'2 = K(COS(1/;2 + 2; ),sin(1/;2 + 2311'),0),
(37.16)
211'. 211'
"'3 = "'(COS(1/;3 - "3),sm(1/;3 - "3),0).
Then, using the experimental fact that the angles <Pi and 1/;i are small, we
obtain the following non-equilibrium energy expression
 = r( "1I + "1~ + "11) + u( "1 I + "1~ + "11)2 + v( "1I"1~ + "1I1J1 + "1~1J1)+
+ V; u[1Jr"1~(<p2 - <pt) + "1I1J1(<p1 - <P3) + 1J~1J1(<P3 - <P2)]+

9
+ 16 WK 6 (1JI1/;r + "1~1/;~ + "1N1)+
+2"Y1K2["1r(<p1 -1/;1)2 + 1J~(<P2 -1/;2)2 + 1J1(<P3 -1/;3)2], (37.17)
where the notation introduced is
The first three terms in the potential (37.17) define the structures to which
the transition from the paramagnetic phase belongs. Just as in the case of
CeAI 2 , we have a 3",-structure for v < 0 and a l",-structure for v > O. In terms
of the quartic OP model the 2",-structure ("11 =
1J2 =I 0, "13 0) is unstable; =
however, as first suggested in [36], non-equilibrium energy terms associated with
wave-vector and magnetic moment orientation may render this phase favorable.
These are the last three terms in the expression (37.17). The coupling of
the wave-vectors and magnetic moments to the symmetric directions (that is,
the tendency of the wave-vectors and magnetic moments to align with the
symmetric directions) is described by the two terms next to last in the potential
(37.17), and their relative position by the last term.
A further task is to eliminate the angular variables in the non-equilibrium

energy. Minimization of equation (37.17) with respect to the angles yields the
two relations:
¢i = (1 + 9w 3;:J 1/';, (i = 1,2,3), (37.19)
4u 2 2
1/'1 = 3v'3WII: 6 (772 - "73) for "71 '# 0 (37.20)
(the expressions for 1/'2 and 1/'3 result from equation (37.20) by cyclic permu-
tation of the indices 1,2,3). The equation (37.20) tells us that only in the
2~-structure are the angles ¢ and 1/' non-zero. Thus deviation of wave-vectors
from symmetric directions is a distinctive feature of the 2~-structure in the
model (37.17).
It is a simple matter to see that on minimizing with respect to the angles,
the last three terms in equation (37.17) are equivalent to the following sextic
invariant:
- 8 ["712( rh2 - "732)2 + "722( "712 - "732)2 + "732( "712 - "722)2] , (37.21)
where
u2 ( 9WII:4) u
WII:36 +
8=- 1 32 - ' -6~1. (37.22)
/1 WII:
From a general analysis of the thermodynamic potential for a 3-component
OP ("71, "72, "73), it follows (see §§17 and 18) that the phase ("7 "7 0), which is un-
stable in the "7 4 model, is stabilized by terms of degree six. The inhomogeneous
terms of the model (37.12) lead to such sextic terms in the effective potential.
Note that, in addition to the invariant (37.21) obtained, the non-equilibrium
energy potential doubtless contains also other sixth-degree invariants, which we
have omitted at the very outset (see equation (37.14)). Adding these invariants
entails no fundamental changes in the results. It might be well to point out that
by virtue of the condition stated in equation (37.22), anomalous large values
of the parameter 8 are required for the quantity W to be sufficiently large.
As a result of minimizing with respect to amplitudes, we obtain three
magnetically ordered phases:
(37.23)
3~ : (37.24)
(37.25)
340 CHAPTER 9
one of which corresponds to the 2~-structure. First-order phase transitions take

place between the 1~- and 2~-structures, and also between the 2~-structure
and the 3~-structure; these transitions occur on the lines r = -v(u+ ~ )(28u)-1
and r = v(u + %)[68(u + ~)tl respectively. The phase diagram is presented
in Fig. 9.12. Inspection of the diagram shows that the 2~-structure may arise
only by two successive phase transitions, a fact that is observed experimentally.
If(
r-J
Fig. 9.12. Phase diagram for the functional (37.12) describing the
multi-~-structurein Nd.
Thus the foregoing thermodynamic analysis shows that only the 2~-struc
ture is accompanied by deviation of magnetic moments and wave-vectors from
the symmetric directions. Experimental observation of this deviation provides
ponderable supportive evidence for the 2~-structure in Nd. Another indirect
confirmation might be the predicted singularities in the excitation spectra of
2~-structures in the vicinity of the phase transition point [30].
Summarizing, the above analysis of whether multi-~-structures may exist
in modulated phases shows that the conditions for such structures to occur are
difficult to fulfill. This is because it is required that the parameter u (that
is, the coefficient of the fundamental 174 term) be small compared to terms of
order w,,4 or Wi ,,6, where wand Wi are the coefficients of the corresponding
invariants describing the inhomogeneous anisotropy.
38. Incommensurate Phases in External Fields
HELICAL STRUCTURE IN AN EXTERNAL FIELD
In this section we deal with various aspects of the behavior of modulated struc-
tures subject to external effects. We start by considering an SS structure, which
is a modulation of a ferromagnetic structure. Assume that this structure is

placed in a magnetic field applied in the plane perpendicular to the wave-vector.
If the structure is described by a two-component OP (1], e) with components
1] and e corresponding to the magnetic moment circular projections AI+ and
M_, then the system's energy described by the Ginzburg-Landau functional
will contain an extra term:
(38.1)
The behavior of the system will depend largely on whether or not the symmetry
allows a Lifschitz invariant. In the first case the functional (36.1) describes, for
n = 1, a helix (spiral) in the field applied in the basal plane, the anisotropy
constant w needing to be identified with H. All the SS structure deformation
effects that arise as the field is varied are described by the solution (36.7) for
n = 1. Clearly, as the field is increased the SS structure deforms; when H = He
(which corresponds to re = 1) it transforms to a ferromagnetic structure. The
transition to this phase proceeds via the soliton lattice, when the change in
magnetic moment orientation along the field is extremely non-uniform.
In the case of an exchange helix, that is, in the absence of Lifschitz in-
variants, the behavior of the SS structure in an externally applied magnetic
field was earlier investigated within the framework of the Heisenberg micro-
scopic model in a number of papers [37], and it was shown that in some critical
field He the helical structure transforms to a fan phase. We now explore this
problem in terms of phenomenological theory using the functional
(38.2)
The natural crystalline anisotropy in the basal plane is disregarded. The min-
imization equation for 1] is of the form
(38.3)
similar to the equation for e.

In the absence of a field an exact solution (35.27) of this non-linear equation
(pair of equations) exists; this is a solution with one harmonic. In low fields
the asymptotic solution has the structure
L
00
1] = Apeipl;;z, (38.4)
p=-oo
342 CHAPTER 9
that is, it contains all multiple harmonics with all p values, the smallness of
the amplitude being defined by the relations
(38.5)
Using the technique described above, we find the wave-vector of an IC

structure in the field:
A2
~2 = ~6 [1 - 12 A~] . (38.6)
The field dependence of the wave-vector is determined by the amplitude of the

first multiple harmonic; in this case AYA~ '" H2.
Thus the helical structure in low fields suffers only a slight distortion which
is described by the occurrence of multiple harmonics and a decrease of the
wave-vector. In a very large critical field He the 55 structure should evidently
collapse and a state with homogeneous magnetization along the field arises. At
H 2: He the OP contains only one zero harmonic Ao, which is determinable
from the cubic equation
rAo+2uA~+H=0. (38.7)
In subcritical fields H < He an inhomogeneous state arises which is usually

called a fan structure. To find this state, we use another aSymptotic limit: We
try a solution of equation (38.3) in the form of a power series in u, retaining
the field term in the zero-approximation equation which has an exact solution
of the form
TJo= A a + A ie il<z + A - i-il<z
e. (38.8)
e
The non-linear term'" UTJ 2 generates new harmonics which are found from the
energy minimization procedure. The least energy is possessed by the solution
with the symmetry
(38.9)
We concentrate on this solution. The amplitudes Ai, A2 and Ag for it are

defined by the expressions
A2 __ L(~) - 2uA5 A _ 4uA~Ao 4uA~

1 - 6u ' 2 - L(2~) , Ag = L(3~)' (38.10)
while the amplitude of the zero harmonic (magnetization) satisfies the cubic
equation
2 10
[r - 3L(~)lAo + "3uAg + H = 0, (H < He). (38.11)
Combined with the equation Al = 0, this equation determines the line of the
phase transition to a homogeneous-magnetization state on the (T, H) plane.
In explicit form the phase transition line is given by the pair of equations:
-L(x;) + 2uA6 = 0, rAo + 2uA~ + H = 0. (38.12)
The wave-vector of the IC phase near this line depends on Hand T through
the amplitudes Ao and A l :
x;
2= X;o2[ 1- P(2x;)
192u 2 22]
AlAo . (38.13)
The spatial distribution of magnetic moment density projections is given

by the expressions
Mx = 'f/ + e= 2Ao + 4A2 cos 2x:z + ... , (38.14)

My = i('f/ - e) = -4Al sin x:z - 4A3 sin 3x:z + ... ,
which parametrically define the relation between the components Mx and My

(hodograph). In high fields the hodograph is an open curve (a segment of a
parabola) described by the extremity (end) of the vector M(z) moving uni-
formly along the z axis. This is what describes the fan structure. Earlier the
fan structure was defined so that the extremity of the vector M(z) moves along
a segment of a straight line perpendicular to field. The straight line is converted
to a parabola by the term with the harmonic A 3 ; this term should be taken into
account since A2 and A3 are of the same order of magnitude. In weak fields
the hodograph is a closed curve. In intermediate fields He ,. .,
[L(O) - 2L(x:)]A l
the topology of the hodograph changes and this point, from all appearance, is
a phase transition point.
EFFECT OF EXTERNAL FIELDS ON THE WAVE-VECTOR OF INCOMMENSURATE

PHASES
In the foregoing we already considered the change of the wave-vector of a simple

helix in a magnetic field applied in the spin rotation plane, that is, in a direc-
tion perpendicular to the wave-vector. The wave-vector decreased in magnitude
with increasing field (in both cases, namely, in the presence of free-energy Lifs-
chitz invariants and in their absence); however, the vector orientation remained
unchanged for a given geometry. The analysis performed may be generalized
in two aspects, by considering magnetic fields with general orientation relative
344 CHAPTER 9
to the wave-vector, and also by applying other physical effects, for example
deformation [38,39], to the system.
If the field is applied in an arbitrary direction to an IC structure wave-
vector oriented, say, in the z direction, then the symmetry may sometimes
admit gradient invariants along another direction, thereby leading to instabil-
ity of the phase with the original wave-vector orientation. An instability will
appear, for example, if invariants of the form
(38.15)
are allowed. The occurrence of such an invariant will cause the wave-vector to
deviate in the x direction. The character of this deviation depends on whether
the parent structure is commensurate or incommensurate. If the structure is
commensurate, an energy of commensurateness exists in the functional <1>; this
energy is described by the invariant wert + en). In the approximation of a
constant modulus of p for the OP the equilibrium distribution problem for the
o P in a field is evidently described by the functional
(38.16)
which, as a matter of fact, coincides essentially with the functional (36.3) con-
sidered earlier. The solution of the corresponding variational problem has the
form [40] (see equation (36.7))
const, HxHz:::; H'6
<P ()
x - { (38.17)
- ~am(qx, re), Hx ·Hz ~ H'6,
where
(38.18)
Thus a certain threshold value of the quantity HxHz exists up to which the
commensurate structure (this may be a normal ferro- or anti-ferromagnetic
structure or a modulated structure with a commensurate wave-vector) is pre-
served owing to the energy of commensurateness. As the threshold is elevated,
a modulation in the x direction arises in the system which is described by the
formula (38.17). From the same formula, it is seen that if the initial structure
is incommensurate, then the modulation in the x direction is induced by the
skew-oriented field in a threshold-free fashion.
We wish to indicate other fundamental possibilities of controlling the wave-
vector by a magnetic field through invariants of the type
(38.19)
d17 de
da{3Ha H{3 dz dz· (38.20)
The first of these possibilities for a modulated anti-ferromagnet in which the

modulation is due to a Lifschitz invariant was noted in [6]. If the field is applied
in a spin rotation plane that is perpendicular to the anti-ferromagnetic wave-
vector Ko, then the invariant (38.19) describes a field-induced second-order
anisotropy which, by the mechanism treated in §36, may lead to the wave-vector
K value changing to the commensurate value Ko. An invariant of the type
(38.20) leads to an immediate change of the constant 'Y in the functional, this
constant determining the value of the wave-vector. A generalized expression of
the form
01]
Da{3,,!oHa H {3 ax"!
oe
ox o (38.21)
contains the possibility that not only the value of the wave-vector but also
its direction may vary. It is clear that a skew-oriented field relative to the
vector Ko should inevitably rotate the latter since the symmetry of the crystal
plus field system no longer reflects the 'good' wave-vector orientation. For an
incommensurate structure this rotation will take place in a field as weak as
desired; for a commensurate structure it should start with some threshold.
Similar effects should arise also when the system is subject to other ex-
ternal effects, for example in the presence of a deformation. The role of these
effects may be illustrated by one good example. At TN = 21 K there arises
in the cubic crystal ZnCr2Se4 a helical magnetic SS structure in which the
wave-vector lies along the cube edge and is close to the vector Ko = (OO~) [41].
The magnetic phase transition here is of first order and is accompanied by the
occurrence of a spontaneous deformation in the direction of the wave-vector.
As the temperature is lowered the wave-vector of the helix varies in strict pro-
portion to the lattice parameter ratio specifying the magnitude of strain. This
linear relation between K and cia may be shown to arise from the symmetry
of the system. ZnCr2Se4 has a spinel structure and the magnetic atoms of
Cr occupy the positions 16( d) of the space group Ok. The magnetic modes
of an anti-ferromagnetic structure with Ko = (OO~) were enumerated in [26].
Comparison of these modes with the observed SS structure shows that the SS
structure is a weak modulation of the collinear anti-ferromagnetic structure
described by two two-dimensional IR's 1"1 and 1"2 of the vector Ko group. With
(1]11]2) denoting the OP components that transform by 1"1 and with (66) rep-
resenting those transforming according to 1"2, we can obtain a functional [or a
four-component OP. The functional contains a Lifschitz invariant that involves
346 CHAPTER 9
the basis functions of both irreducible representations:
d'f/1 d6 d6
rr ( 6 - -'f/1- +'f/2-
dz dz dz
- 6d172
-) .
dz
(38.22)
Also there exist two invariants that contain the strain tensor component (zz:
(38.23)
The SS structure observed in ZnCr2Se4 is described by the following assignment

of the OP components:
'f/1 = 'f/ SlDKZ , 6 = 'f/COSKZ, 'f/2 =6 = o. (38.24)
For this class of solutions the problem of determining the equilibrium structure
reduces to one of minimizing the functional with a one-component OP that
interacts with the strain (zz:
(38.25)
This gives the value of the wave-vector K and the magnitude of the spontaneous
deformation (~z:
11,=-
rr + (3(~z , (38.26)
2,
o
(zz
1( rr)2 2 r
= -2L 6- 2,(3 'f/, 'f/ ~-2u· (38.27)
It is the equation (38.26) that demonstrates the linear relationship between 11,
and (~z, a relationship that is due to the invariants (38.22) and (38.23).
Eliminating the quantity (zz from the expression (38.25) leads to the renor-
malization u ---+ u - ft(6 - {,(3); as a result of this renormalization the u may
become negative, which would lead to a first-order transition. Indeed, a first-
order transition is observed experimentally. However, no unambiguous conclu-
sion may be drawn concerning the mechanism involved. This is because in the
presence of a magnetostriction the magnetic fluctuations, which are not taken
into account in this calculation, also result in the phase transition changing
from second order to first order.
It is noteworthy that the crystal ZnCr2Se4 is a rare example where mag-
netic structure modulations are due to Lifschitz invariants. In spite of the high
symmetry of this crystal, the linear invariant with respect to gradients exists
owing to the participation of two irreducible representations. Such invariants
are known to describe the energy of small relativistic interactions, so the modu-
lation which they bring about should be small too. In fact, the angle of rotation
of spins on two adjacent crystal planes in ZnCr2Se4 is 42 0 at T = 4.2 K [41].
If this angle were exactly 45 0 , this would correspond to an anti-ferromagnetic
structure with the wave-vector Ko = (OO!); from this, it is clear that the
modulation vector '" is very small. Other examples of modulated magnetic
structures due to Lifschitz invariants are the isomorphous compounds MnSi
and FeGe. These two compounds have a space group T that contains no center
of inversion. In both crystals the modulation vector is also very small [42].
Similar behavior persists also in purely structural modulations of the crystals
[43].
39. The Thermodynamics of Phase Transitions

to Incommensurate Phases
CONSTRUCTING A THERMODYNAMIC POTENTIAL FOR NON-LIFSCHITZ STARS
In a specific exploration of a phase transition going over a wave-vector non-

Lifschitz star, the usual problem arises of constructing a thermodynamic po-
tential. Method!'; of constructing polynomial invariants for Lifschit.z stars were
outlined in detail in Chap. 4. Unfortunatley, the IRBI construction technique
described there may not be applied for non-Lifschitz stars with an arbitrary
wave-vector on some line since the corresponding I group is insoluble and the
method described rests on theorems of soluble groups. In this situation one
has to exploit the straightforward method, in which the initial-phase symmetry
group generators act on an arbitrary polynomial of a given degree constituted
by OP components, requiring that the polynomial be invariant. For phase
transitions to incommensurate phases described by non-Lifschitz stars there
are some peculiarities in the construction of thermodynamic potentials. These
peculiar features can be readily illustrated by a particular example.
Consider the familiar phase transitions in the K2Se04 crystal [44]. This
compound exhibits a sequence of two phase transitions: At Tl = 130 K the
initial-symmetry crystal suffers a structural second-order phase transition ac-
companied by formation of an incommensurate phase; at T2 = 93 K a second
phase transition occurs which gives rise to a commensurate phase and leads si-
multaneously to a spontaneous-polarization jump. This second transition thus
is a first-order phase transition. The presence of a structural transition at the
point Tl has been revealed by X-ray and neutron diffraction. In both cases
348 CHAPTER 9
the crystal displayed at T < T1 superstructural satellites lying in the direction

of one of the reciprocal-lattice unit cell edges (near the value b/3). The su-
perstructural wave-vector, which varies with temperature, may be represented
as
Kf!.. = (1 - A)b/3, (39.1 )
where A = 0.07 in the vicinity of T1 and decreases as the temperature is low-
ered [44]. At the point T2 the value of A goes abruptly to zero; consequently, a
=
commensurate phase arises that has wave-vector", b/3; this vector already
does not vary with further decrease in temperature. Thus an incommensurate
to commensurate phase transition takes place at the point T 2 . The commen-
surate phase becomes an improper ferroelectric.
A neutron diffraction study [44] has shown the first structural transition
at the point T1 to come from the instability of the transverse optical phonon
mode of symmetry I:2 in the parent crystal with the wave-vector parallel to b
( direction of the z axis in the Brouillon zone). A complete softening of a phonon
with wave-vector q ~ b/3 was observed at T - T 1 . It is the condensation of
this phonon at T < T1 that produces an incommensurate phase in K2Se04 over
the temperature range T1 > T > T 2 •
Construct the thermodynamic potential corresponding to the symmetry of
the soft phonon mode. To find the space group IR matrices, we use Kovalev's
tables, in which the group D~~ is denoted Pmnb (in the International Tables
this is the group Pmna). In Kovalev's notation the wave-vector (39.1) of the
superstructure is
(39.2)
and belongs to the two-arm star {",8}. The wave-vector group has four one-
dimensional IR's: 71(I:t), 72(I:2), 73(I: 4), 74(I:3). By the formula (2.7) we
induce the representation matrices of the entire group D~~. The IR's of interest,
72 and 74, are written out in Table 9.1.
From Table 9.1, we find how the OP components 1]1 and 1]2 transform
under the action of the group generators h2' h3, and h 2S :
h21]1 = -1]2, h31]1 = e- i7rJ1 1]l , h2s 1]1 = 1]2,

(39.3)
where J-l = (1 - A)/3.

It is now easy to verify that the expression 1]11]2 is an invariant of the group.
Higher-order invariants, except the trivial (1]11]2)2, should be constructed allow-
ing for the preservation of the total wave-vector (to within the reciprocal lattice
Table 9.1
Irreducible representations of the group Pmnb for the star of the wave-
vector "'- = lib 2
v hllO h21Ho h310 H h41~O~ h2S IHO Ih26 10 h271~O~ h28 10 H

1 0 o -1 _e- i1r /-l 0 0 _e i7r /-I 0 1 -1 0 0 ei1r/-l _e- i1r /-l 0
72
0 1 -1 0 0 e i1r /-I _e- i1r /-l 0 1 0 o -1 e- i1r /-I 0 0 _ei 1r /-I
1 0 o -1 _e- i1r /-l 0 0 _ei'lr /-I 0 1 1 0 0 _e i7r /-I _e- i7r /-I 0
74
0 1 -1 0 0 _e i1r /-l _e- i1r /-l 0 1 0 0 1 _e- i1r /-l 0 0 _e i1r /-l
vector). In the case of an arbitrary Ii (incommensurate phase) no power invari-

ants exist for the quantities TJl or TJ2' Invariants may exist if there is one more
two-component quantity (xt[, X2) that is specified by a wave-vector of the same
symmetry but with a different value of Ii. For example, if Xl is assigned to the
wave-vector
(39.4)
and X2 is assigned to the vector (-"'-3a), then the law of conservation of wave-
vector will be fulfilled in the expressions 17rXl and TJ~X2 since "'-a + "'-3a = b 2 .
When .6. --+ 0 the wave-vector "'-3a --+ 0 and the corresponding quantities Xl
and X2 need to be identified with the spontaneous polarization arising in the
direction of the c axis; from this, it follows that they should transform according
to the IR 74(E 3) [44].
From Table 9.1 we obtain the transformation laws for the quantities Xl
and X2, similar to the relations (39.3):
h = -X2,
2Xl h 3Xl= e -i1r/-l Xl, h
= X2,
2SXl
(39.5)
h2X2 = -Xl, h3X2 = -e i1r /-lX2, h2SX2 = Xl,
where Ii = .6..
It can now be readily verified that it is the quantities XlX2 and TJrXl + 1J~X2
that are invariants. Thus we have the following expression for the thermody-
namic potential describing the phase transitions in K2Se04:
(39.6)
350 CHAPTER 9
This expression contains only one coefficient that reverses sign as the tem-
perature is varied, namely, rj this is because 17 is a vrai OP that describes
a definite atomic displacement in the crystal. The other coe~cients depend
weakly on temperature. The concomitant OP x describes a polarization wave
with wave-vector (39.4).
PHASE TRANSITION FROM INCOMMENSURATE TO COMMENSURATE PHASE
The thermodynamic potential coefficients (39.6) may depend not only on tem-
perature, but also on the magnitude of the superstructureal wave-vector or
on the parameter 6.. We assume the following rand '" dependence of the
coefficients T and 6.:
(39.7)
(39.8)
where 6. 0 is the value of 6. at the point T = T 1 • The relation between the OP
17 and x leads to the quantity .6. depending on temperature. To determine this
dependence, we need to minimize the potential (39.6).
We rewrite the expression for the potential, separating the modulus and
the phase in the complex OP 17 and x:
(39.9)
We have
(39.10)
Minimization with respect to the phase yields 3¢+1/J = 0, so that cos(3¢+1/J) =
±1 (the sign is chosen as a function of the sign of 6). Minimizing the expres-
sion (39.10) with respect to x gives a relation that expresses the concomitant
parameter in terms of the vrai OP:
(39.11)
On eliminating x in the expression (39.10), we find an effective potential that

contains only a vrai OP:
<Jl= r172+u174+ (v- 6:)17 6 . (39.12)
Confining ourselves to a degree of 17 not higher than four, we find
r )1/2 1/2
17:::::: ( - 2u '" (T1 - T) . (39.13)
Allowing for this expression, equation (39.11) now gives the temperature de-
pendence of the concomitant OP:
(39.14)
The temperature variation of the wave-vector may be obtained by mini-

mizing the potential (39.12) with respect to the variable ~. From the equation
[)iJ>I[)~ = 0, we obtain the expression
(39.15)
which gives the observed decrease of ~ with decreasing temperature if the

parameter {3 < 0. At the point T2 of the phase transition to a commensurate
phase the quantity ~ undergoes a discontinuous change from ~o[l + A(TI -
T2)2]-1 to zero; in this case the polarization wave described by the concomitant
OP x with the wave-vector ~b2 transforms into a continuous polarization. To
determine the polarization that suddenly arises at the point T 2 , terms giving
the polarization energy and the relation to the OP TJ and x should be included
into the thermodynamic potential.
CONCOMITANT ORDER PARAMETERS AND INCOMMENSURATE·PHASE

SYMMETRY
As the temperature is varied over the interval Tl > T > T2 the wave-vector
n, = f.lb 2 of the incommensurate phase runs over a sequence of rotational values
of f.l = min. The set of numbers m and n determines the symmetry of the
corresponding phase. The number n specifies the invariants under the initial-
phase translation group. For a two-component OP {TJITJ2} (with TJ2 = TJn
there are two such invariants: TJ? and TJ~. From these, we may set up two real
invariants:
(39.16)
Under the operation of the rotation elements of the initial-phase symmetry

group these quantities will transform, the transformation laws depending also
on the number m [45].
\Ve wish to see, for example, how the quantity TJr + TJ~ transforms under
the operation of the element h 3 . Using the relations (39.3), we write
352 CHAPTER 9
whence it is clear that in the case of even numbers m the quantity TJ'1 + TJ~
remains invariant, while when m is odd this quantity changes sign. Results
of a similar analysis for all group Pmnb elements are consolidated in Table
9.2. The last column of the table contains combinations of x, y, z coordinates,
which transform in a similar fashion. The results of Table 9.2 tally with those
of [45] after an appropriate coordinate permutation associated with a different
orientation of the group D~~. The authors of that paper were the first to
indicate that macroscopic properties should exist in the incommensurate phase
which are determined by the transformation laws for the quantities TJl ± TJ2'
Table 9.2
Transformation of the quantities TJl ± TJ2 under the operation of the
group Pmnb elements
h2 h3 h4 h25 h26 h27 h28
TJl + TJ2 n even 1 -1 -1 1 1 -1 -1 yz

TJ"i - TJ2 m odd -1 -1 1 -1 1 1 -1 z
TJl + TJ2 n odd -1 -1 1 1 -1 -1 1 xy
TJ"i - TJ2 m odd 1 -1 -1 -1 -1 1 1 x
TJ"i + TJ2 n odd -1 1 -1 -1 -1 1 -1 xz
TJ"i - TJ2 m even 1 1 1 -1 -1 -1 -1 xyz
Notation: TJl and TJ2 transform by the two-dimensional IR T2 with the

wave-vector K, = ~b2
Indeed, examination of Table 9.2 shows that, for example, the quantities
(TJ"i + TJ2)fyz and (TJ"i - TJ2)PZ are invariant (for even n and odd m), where
fyz and Pz are the components of some second-rank tensor and a polar vector.
Therefore the occurrence of an incommensurate phase with condensed OP's TJl
and TJ2 may induce relevant macroscopic properties in the crystal. When the
parity of nand m changes, as can be seen from Table 9.2, the components of the
macroscopic quantities undergo changes or new quantities appear. It stands to
reason that these quantities may have appreciable values only at small n since
the invariants responsible for their occurrence have smallness", TJ n . From what
has been stated above, it follows that individual steps in the devil's staircase
of transitions may be registered on detecting macroscopic properties of the
incommensurate phase. In principle, there may also exist wave-vector 'lock-
in' mechanisms due to the occurrence of one of the macroscopic quantities
conjugate to r/i ± 17~ .
PECULIARITIES OF SUSCEPTIBILITIES IN INCOMMENSURATE PHASES
Pursuing our study of the macro characteristics of the incommensurate phase,

we consider the behavior of susceptibilities corresponding to concomitant macro-
parameters [45]. We can now tear ourselves away from our example with
K2Se04 and consider the problem in a more general statement. Let there be
some phase on the devil's staircase of transitions with wave-vector,., = (m/n)b,
that is, with a period that is a factor of n larger than the initial-phase period.
As we saw in the foregoing, the OP components 171 and 172 may be used to
construct two invariants (39.17), l7n cos n¢ and l7n sin n¢, under the translation
group. We consider two macroscopic quantities Xl and X2 that transform un-
der the action of the crystal initial-phase group in a similar way and write the
thermodynamic potential, including the fields Xl and X2 conjugate to these
quantities:
q, = r172 + U174 + W172n cos 2n¢ + 8117n cos n¢x1 +

+8 217n sin n¢x2 + K1Xi + K2X~ - X1X1 - X2X2. (39.17)
The quantity 172n cos 2n¢ may be viewed as the square of anyone of the quan-
tities (39.16) and is an invariant since these quantities themselves transform
according to one-dimensional representations.
Minimizing q, with respect to Xl and X2 yields the equation of state
(39.18)
with the help of which we can readily eliminate the variables Xl and X2 from
the thermodynamic potential and write it in the form
(39.19)
354 CHAPTER 9
where
81
W=W _ _
2
+_2.
82
8~1 8~2
We start by finding the equilibrium values of 1] and cjJ in the absence of
the fields Xl and X 2 . To lowest order in 1] the condition 8, Ph/81] = 0 yields
the result 1] ~ (-r /2u )1/2, and the condition 8<1.? / 8cjJ =
0 gives sin 2ncjJ =
0 or
cos 2ncjJ = ±l. The choice of the sign depends on the sign of the parameter w.
For w < 0 we have cos2ncjJ = -1 and the expression (39.19) yields
(39.20)
For w > 0 we have cos 2ncjJ = 1 and

(39.21)
Thus for a given 1] a phase is possible in which only one of the macroscopic
quantities Xl or X2 arises spontaneously, the temperature dependence of that
phase being determined by the value of n:
(39.22)
Consider now the susceptibilities XAI' = dx)../dX w Using equation (26.12),

the respective results for w > 0 and w < 0 are
(39.23)
Xll = (2~d
-1
+
8r
16 2 - ,
~lW
(39.24)
-1 8~n2 2n-4
X22 = (2~2) + 32u~~ 1] .
Because of the smallness of 1], the susceptibilities Xll in equation (39.23)

and X22 in equation (39.24) at large n are virtually the same as those in the
initial phase: 1/2"'1 and 1/2"'2. As for the susceptibilities X22 in equation
(39.23) and Xu in equation (39.24), they do not depend on 1] and therefore
their discrepancy from the value in the initial phase is of the same order of
magnitude as the value in the usual second-order phase transitions. This prop-
erty is inherent in only one of the susceptibilities, which corresponds to that
macrovariable x whose spontaneous value in a given phase is equal to zero.

With varying nand m the macro quantities Xl and X2 and, consequently, the
relevant susceptibilities acquire a different physical meaning.
This result therefore implies that in moving along the devil's staircase,
some susceptibilities should undergo sudden appreciable discontinuous changes.
As noted by the authors of [38], considerable difficulties may be encountered
in the experimental detection of susceptibility jumps at transitions between
phases with large n: A whole set of long-period phases with different wave-
vectors N- may exist in the crystal owing to the various inhomogeneities present
in it.
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356 CHAPTER 9
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CHAPTER 10
Color Symmetry and its Role in

Phase Transition Theory
40. Color Symmetry in the Theory of Magnetic Structures
MAGNETIC STRUCTURES AND THEIR SYMMETRIES. GEOMETRIC ASPECT
The space groups were introduced for describing the symmetry of crystal struc-
tures. A crystal structure is a spatially ordered collection of atoms. The relative
position of atoms defines the symmetry of a given crystal, that is, a set of ro-
tations, reflections, and translations that map the structure onto itself. The
crystal structure is given by a set of atomic coordinates, and these coordinates
are the only entity on which the symmetry elements act.
In describing magnetic structures, one needs already two sets of variables,
namely, the coordinates of magnetic atoms l'i and the spin direction Si. The
new variable Si permits introduction of specific magnetic groups to describe
the symmetry of magnetic structures. Take any magnetic structure M, for
example, the structure of the garnet Mn3Al2Si3012 (see Fig. 2.6). Evidently,
if we reverse all spin directions without permuting the atoms as we do so, the
energy of the system will not change and the new structure M' will have the
same symmetry as that of the parent structure M. The structures M and
M' may be viewed as two domains. An element that transforms the structure
All into M' is the spin inversion, which is normally denoted by the symbol I'.
Therefore the symmetry group of the initial phase should contain, in addition
to the usual spatial symmetry elements g, elements of the form g I'. A set of
elements g and gl' constitutes a group H = G X 1', where the symbol l' is used
to designate the spin inversion group I' = {l, I'}. The various combinations of
elements g and I' generate a set of what is known as Shubnikov groups, which
contains 1651 magnetic space groups [1].
358
COLOR SYMMETRY IN PHASE TRANSITION THEORY 359
As already noted, the introduction of Shubnikov groups is based on the

presence of two variables, ri and Si, which describe any magnetic structure,
and on the possibility of a reversal of spin with the atomic coordinates remain-
ing unchanged. Such restriction in the choice of rotations of spin variables
counts in describing the symmetry of incommensurate structures. Thus at-
tempts to describe the symmetry of such structures with the help of Shubnikov
groups lead to trivial identity groups. This can be readily demonstrated with
the example of the symmetry of a magnetic structure such as a simple helix
with wave-vector K, = (OOX: z ); such a structure is realized, for example, in the
spinel ZnCr2Se4 (space group oD. If we make use of Shubnikov groups, the
symmetry of such a structure is described by elements {hdO} and {h4iO} and
by translations along the x - al and y - a2 axes [2]. But the spatial arrange-
ment of spins, which corresponds to the structure involved, has a clearly visible
higher symmetry. Shubnikov groups are inapplicable because their elements do
not contain rotations of atomic spins by an angle </>, which is determined by
the pitch of the helix. If we introduce the corresponding rotations of the spin
variables into the set of symmetry elements used, we can obtain magnetic color
groups [3-6].
With the spinel ZnCr2Se4 we have, in addition to the elements already
enumerated, the translation {hlia3i</>z}, the elements {h 2 iOi1Tx}' {h 3 iOi1Tx }'
{hdTi~</>z + 1Tx}, {hl4iTi~</>z}, {hl5iTi~</>z}' and {hl6iTi~</>z + 1Tx}, and also
eight more elements. The latter are obtained by multiplying the preceding
elements by {h25irlt</>z + 7r x }. The notation adopted here is as follows. The
first place is occupied by a spatial point element and the relevant non-trivial
translation T = (~ ~ ~), which act on the coordinates of atoms. Next come
symbols that indicate the angle of rotation of the spin variables about the
corresponding axis. The angle </>z (rotation through an angle </> about the z
axis) is determined by the pitch of the helix.
The term 'color groups' reflects the fact that not only space group elements
but also sets of rotations </>i of atomic spins participate in the formation of
these groups. By analogy, Shubnikov groups may be called black-and-white
groups since the extra spin inversion element I' may be viewed as one additional
rotation of atomic spins by 180 0 •
An arbitrary Shubnikov group element may be written in the form
gQ = g(r, S)</>(S). ( 40.1)
This representation means that the first factor, which is an element of the
space group, changes the coordinate of the atom and inverts its spin. The
360 CHAPTER 10
second factor changes only the direction of the atomic spin and is due to the
extra element I' included in the Shubnikov group. Groups whose elements have
the form (40.1) are called Q groups [7].
Evidently, the action of symmetry elements of magnetic color groups may
be entirely separated into atomic coordinates and atomic spins:
gp = g(r)tP(S). (40.2)
The first factor, which acts on the atomic coordinates, will be called a base
element. The second factor will be called an element of load or simply a color
load. Groups with elements in the form of equation (40.2) are customarily
called P groups. The above color group for ZnCr2Se4 is an example of such a
P group.
The P and Q groups were obtained when introducing additional rotations
of all crystal spins simultaneously by the same angle tPi. A further complication
of the color groups is the introducion of an individual angle of rotation tP for
each spin. As a result, we obtain W type color groups [8]. Proceeding from the
way the elements of these groups operate on spins, we may, by analogy with
the foregoing, introduce the WQ and Wp groups:
(40.3)
Here the subscript r of the operator tPl.(S) denotes that the rotation of each
spin S depends on the spin coordinate r.
The introduction of color groups was motivated by the problem of classi-
fying magnetic structures [3], a necessity which predetermined the geometric
method of introducing these groups. Later it was shown [9-11] that apart from
an obvious classificatory content, the color groups have also a certain phys-
ical meaning associated with the symmetry of the thermodynamic potential
employed to describe a magnetic phase transition.
COLOR SYMMETRY AND THE THERMODYNAMIC-POTENTIAL MODEL
Consider a thermodynamic potential that describes a magnetic phase transition

from a paramagnetic phase to some magnetically ordered phase. As variables
we will temporarily use components of atomic spins Sf ((l' = x, y, z). We write
down the potential ~ and require that it be invariant under the elements of
the crystal space group G in the initial phase. Evidently, such a potential will
contain invariants of a different physical nature, that is, terms that correspond
to an exchange interaction, one-ion and crystalline anisotropy, etc. The powers

of the quantities Sf involved in the potential cI> are even. Therefore, besides
being invariant under the space group G, the potential cI> will be invariant also
under an inversion of spin I'. Thus we come to the Shubnikov groups G x I' for
describing the paramagnetic phase. It may be concluded that the machinery
of Shubnikov groups implies a 'model-less' description of magnetic structures,
that is, it implies allowance for all the kinds of interaction in the formation of
these structures [12].
In the 'model-less' potential so constructed, we now leave only the in-
variants that are of an exchange nature, that is, invariants of the form (SiSj)n.
Evidently, besides being invariant under the elements of the group G and under
an inversion of spin 1', the potential cI> will be invariant also under a simul-
taneous rotation of spins by an angle ¢. In the exchange approximation, the
group of the paramagnetic phase may be represented as M = G x 0(3), 0(3)
being the rotation group (see, for example, [13]). The exchange group belongs
to P-type color groups. The properties of these color groups were investigated
in detail in [10] and [11].
Vlfe may construct in the same way the color group corresponding to the
one-ion and crystalline anisotropy [14].
Note that the symmetry of the potential cI> is determined by two consid-
erations. One of them consists of choosing a model, that is, throwing away
weak interactions. The other consideration lies in throwing away higher-degree
invariants (see §14). In the present section all the arguments that relate to
imparting a physical meaning to the color groups disregard this second aspect.
The technique ou tlined above of eliciting the physical meaning of magnetic
color groups rests in large measure on the choice of the potential's variables,
which are atomic spin components Sf. However, such choice of variables is not
constructive in analyzing most of the magnetic phase transitions in crystals that
contain more than one atom per unit cell. More convenient variables are mixing
coefficients of magnetic modes - symmetrized combinations of the quantities
Sf (see §6). With this choice of variables, the direct relation between the
form of individual invariants and their physical nature is lost, becomes latent.
Also, the problem of finding a model potential cI> that involves only part of
the interactions becomes appreciably more complicated. To construct a model
potential depending on OP components, we may exploit the already elicited
physical content of different color groups. In choosing a model, allowance for
certain interactions is implied, while others are disregarded.
362 CHAPTER 10
We wish to illustrate, with an example of FeGe2 type compounds, the most

rational method of constructing a thermodynamic potential that depends on
OP components. The method concerned is based on using color groups of a
definite type.
THE HIERARCHY OF APPROXIMATIONS FOR DESCRIBING THE MAGNETIC

STRUCTURE OF FeGe2
The compounds FeSn2 and FeGe2 have the symmetry D~~. The Fe atoms
occupy the position 4(a); the Sn and Ge atoms occupy the position 8(h). Ac-
cording to available data [15], a collinear magnetic structure Sl S2 -S3 = = =
-S4 = (uvO) arises in FeSn2 at T1 =
378 K. At T2 =
93 K this structure
transforms to a cross-type structure Sl -S2 = =
(uvO), S2 -S3 =
(vuO).=
In FeGe2 an incommensurate magnetic structure [16] is realized in the interval
T2 < T < T1 (T1 = 287 K, T2 = 265 K). At temperature T2 the incommensurate
phase becomes commensurate.
The collinear magnetic structure in FeSn2 and FeGe2 is described by the
wave-vector Ii, = (~OO); the cross-type structure arises from the collinear struc-
ture by adding a mode with Ii, = O. Consequently, a thermodynamic description
of the phase transitions in FeSn2 and FeGe2 will require modes with Ii, = (~OO)
and Ii, = O. Along with the magnetic OP, we will take into account also the
elastic variables. This will enable us to investigate the magnetostrictive effects,
which are sufficiently strong in FeGe2'
We start our investigation of this interrelation between the choice of the
symmetry group of the initial phase and the form of thermodynamic potential
by considering the most general case where all types of interaction are taken
into account. As already noted, in this case we choose as the symmetry group
of the initial phase the Shubnikov group D~~ x I'. The constitution of the
magnetic representation
Ii, = 0:d'M = 73 + 74 + 79 + 710,

( 40.4)
Ii, = 000): d'M = 73 + 74 + 79 + 710,
gives us the starting set of OP's:
Ii, = 0: 79 (7]1'r/2), 710(7]3174), 73(7]5), 74(176);
(40.5)
Ii, = (~OO): 79(6e2), 710 (eae4), 73(e5), 74(e6);
Exploiting the methods outlined in Chap. 4, we can readily construct from
the variables (40.5) a 'model-less' thermodynamic potential. In the fourth-
degree approximation allowing for gradient invariants, this potential contains
around a hundred terms. As the potential has been constructed in terms of

magnetic-mode mixing coefficients (40.5), the physical meaning of the afore-
mentioned coefficients is not clear. To resolve this problem, we make use of
color groups.
In the exchange approximation the initial-phase symmetry group D~~ x
0(3) is a supergroup of the Shubnikov group D~~ x I'. Therefore, if we now
operate with the exchange group elements on the 'model-less' potential already
constructed and require that it be invariant, a considerable part of the invari-
ants will vanish. The rest of the invariants have the form
4
<Jl~ = L ria; + L Uija;a; + L (a1 a i)(aja,,)+
i=l i~j i##l
<Jl~ = C1(U;x + U;y) + C2U;z + C3(U;y + U;x)+

+C4 (U;z + U;z) + C 5 (U;x + U;y) + C6UxxUyy+
+C7 (U xx + Uyy)Uzz + CsUxyUyX + C9(UxzUyz + UzxUzy ), ( 40.6)
4
<Jl~u = L [>'lia;(Uxx + Uyy ) + >'2i a ;UZZ ] ,
i=l
where uex(3 = auex /ax(3, (Ci,/3 = x,y,z),
Ci1x = H1]l + 1]2), Ci2x = ~(1]3 + 1]4),

Ci1y = ~(1]1-1]2)' Ci2y = H1]3-1]4), (40.7)
(the quantities a3 and a4 differ from a1 and a2 in the 1]i being replaced by
ei). The expression (40.7) illustrates the relation of the exchange variables ai
to the original variables 1]i and ei.
A further step is to isolate from among the remaining invariants of <Jl - <Jlo
those that correspond to the single-ion anisotropy approximation. To this end,
we need to determine the group of the single-ion anisotropy and to act with this
group on the invariants of <Jl-<Jl 0 that have remained. The single-ion anisotropy
is normally introduced by adding terms :Jzz Slz to exchange invariants of the
type J;j(SiSj). It singles out one of the directions in the crystal (for example,
the z axis), whereas all directions in the perpendicular plane remain equivalent.
364 CHAPTER 10
In the general case this approximation is evidently inadequate since the single-
ion anisotropy is determined by the surroundings of the given atom.
The equivalent directions on the site i are described by the site group Gi,
which for the Fe atoms in FeGe2 is the group D 4z . In the general case the
group Gi may have a different orientation on each site i of a given position, a
situation which corresponds to a distinct set of equivalent directions on each
site. Allowance for the single-ion anisotropy then reduces to isolating equivalent
directions that are common to all sites and are described by the intersection
of all the groups Gi. As can be readily seen, the single-ion anisotropy in the
example under consideration may be represented as a direct product of the
parent group D~~ and the group Go = D 4z : D~~ x D 4.
Acting with the resulting group D~~ x D4 on the potential <1> - <1>0, we
separate the invariants of <1>' corresponding to the single-ion anisotropy ap-
proximation:
<1>~f = vl7]i7]~ + v2e5e~ + V37]17]27]37]4 + V4e166e4 + VS7]17]2e16+

+V67]37]46e4 + V77]17]26e4 + V8(7]16 - 7]2e2)(7]36 - 7]4e4)+
+V9(7]r + 7]~)7]i + vlo(e5 + e~)e~ + Vll(7]r + 7]~)7]~ + V12(e5 + e~)ei+
+V13(17I + 17~)e~ + V14(e5 + e~)7]~ + V15(7]r + 7]De~ + V16(e~ + el)1]~,
<1>~fu = 617]~( Uxx + Uyy ) + 627]~Uzz + 637]~( Uxx + Uyy ) + 647]~Uzz + (7] --; e).( 40.8)
For the quantity <1>~Iu we have written out only half the terms; the other half
can be obtained if we replace 1]i byei.
The rest of the invariants of <1> - <1>0 - <1>' are determined by the rest of the
interactions and have the form
(40.9)
Thus blocks have been isolated in the potential (40.6)-(40.9) that corre-
spond to the exchange approximation and the single-ion anisotropy approxi-
mation. In similar fashion, we may separate the invariants corresponding to
the crystalline anisotropy. The potential thus obtained may be employed to
describe magnetic and magnetoelastic properties in the exchange approxima-
tion or the single-ion anisotropy approximation. In this way, the authors of
[14] investigated the spectrum of magnetoelastic excitations in FeSn2 for three
models. The magnetic phase transition to the incommensurate phase was in-
vestigated in [17].
'With reference to the example of FeGe2 and FeSn2, we have shown how
a 'model-less' thermodynamic potential, which includes all interactions and is
invariant under the Shubnikov group D~~ x 1', is reduced depending on the
requirement that it be invariant under the exchange group D~~ x D4 X I'.
In practice magnetic phase transitions are investigated within the frame-
work of a particular model and the problem of the hierarchy of the various
model potentials does not arise. Instead, the necessity arises of constructing a
thermodynamic potential that corresponds to the model chosen and depends
on the OP components. The scheme of constructing the necessary potential
here is altered somewhat but continues to rest on the choice of an appropriate
color group, for example an exchange group. For the chosen group we con-
struct exchange modes, to each of which corresponds its own exchange-group
IR, that is, its own exchange multiplet [13]. Next, as usual, we use exchange
mode mixing coefficients (performing the function of OP's) to construct an
exchange potential, all the terms of which are of an exchange nature. Simi-
larly, we may construct a thermodynamic potential in the single-ion anisotropy
approximation, choosing as the parent group the single-ion anisotropy group.
Summarizing, the idea of the interrelationship between the form of the
thermodynamic potential and the type of color symmetry has proved fruitful
not only in the theory of magnetic structures, but also in the description of
incommensurate structures (§41) and superconducting phase transitions (§43)
and in the analysis of quasicrystals (§42).
41. Supersynulletry of Incommensurate Structures
INCOMMENSURATE STRUCTURES AND THE PARADOX OF THE CHESHIRE CAT
'Vith the experimental discovery of incommensurate structures, the problem

arose which in [18] is figuratively called 'the paradox of the Cheshire cat'. This
name seems to be a very happy one since first, surprising properties of in-
commensurate structures were detected and an explanation of those properties
came somewhat later. The paradox arose as a result of attempts to describe
incommensurate structures using the machinery of the space groups. In this
traditional description of the symmetry of incommensurate structures, we ar-
rive at the conclusion that the property of translational invariance, normally
identified with the notion of long-range order, is perturbed in these structures.
On the other hand, experimental X-ray diffraction patterns of incommensurate
structures are three-dimensionally periodic, a fact that contradicts the previous
statement. A similar situation occurs in the case of rotational symmetry. On
the one hand, the observed macroscopic properties of incommensurate struc-
tures indicate the presence of a rather high macroscopic (point) symmetry. On
366 CHAPTER 10
the other hand, when described conventially with the help of space groups, the
orientatjonal symmetry of incommensurate structures reduces, as a rule, to a
trivial identity group.
The problem that has arisen can be solved by use of two major methods.
One of them rests on the use of space group IR's [18,19]. It is this method
that is employed in Chap. 9 to analyze phase transitions to incommensurate
phases. The representational approach is based on the use of transformation
properties of the relevant OP with a rational wave-vector "'0 close to the wave-
vector,., of an incommensurate structure. To ensure that a minimum of the
thermodynamic potential q, exists at the point "', spatial derivatives of the OP
along with homogeneous terms are included in the potential. In principle, the
representational approach enables one to describe all the observed anomalies
in physical properties that accompany the formation of an incommensurate
structure, and also to describe the properties of the incommensurate structure
itself. This approach necessitates no identification of the symmetry group CD
ofthe incommensurate structure. Nevertheless, a knowledge of the group CD of
the incommensurate structure proves useful in a number of cases, for example
in investigating the excitation spectrum of commensurate structures [20], the
light scattering on an incommensurate structure [2], etc.
The other way to solve the paradox of the Cheshire cat is by investi-
gating the symmetry of the incommensurate structures. As noted in [21-25],
incommensurate structures may be viewed as the result of projecting a com-
mensurate multidimensional crystal structure on a three-dimensional space.
Thus the problem of finding the symmetry of incommensurate structures re-
duces to one of finding the symmetry of multidimensional crystal structures,
called supercrystals. The search for the multidimensional symmetry rests on
the symmetry of the diffraction picture and is as follows. Suppose that a given
incommensurate structure is described by one wave-vector,., " b 3 (,., = ~b3'
where m and n are integers). Then the set of reflections in the reciprocal space
should be described by the scattering vector re = hb I + kb 2 + lb 3 + ~b3. This
expression may be viewed as the projection of the four-dimensional reciprocal
lattice given by the vectors b I , b 2 , b 3, and b 4 = ,., + e, where e is the unit
vector orthogonal to the vectors b I , b 2 , and b 3 , on the three-dimensional sub-
space e = O. Accordingly, the scattering vector may be rewritten in the form
re = hb I + kb 2 + Ib 3 + pb 4 . Using the inverse Fourier transform
(41.1 )
with r = (X1X2X3X4), we can restore the density function P(X1X2X3X4) of the

four-dimensional crystal. The corresponding multidimensional symmetry group
is easy to determine from the restored multidimensional density function.
In its essence, the above briefly outlined approach to solving the paradox
of the Cheshire cat is a geometric one. The introduction of color groups to
describe the symmetry of incommensurate structures has solved the problem
of their classification and permits the various properties of these structures,
particularly all the peculiarities of the diffraction pictures, to be described more
completely. The idea that the incommensurate structures are a projection on
the three-dimensional space of multidimensional supercrystalline structures has
proved fruitful and has been exploited to describe quasicrystals (see §43).
As already stated, apart from the symmetric approach, there is also a
representational approach to describing incommensurate crystals. The repre-
sentational approach is based on the IR's ofthe space groups of the initial com-
mensurate phase. Just as with magnetic phase transitions, we may attempt to
relate the color groups to the symmetry of the thermodynamic potential. This
problem was solved in [26].
PHASE SYMMETRY OF THE THERMODYNAMIC POTENTIAL AND THE

SYMl\iETRY OF INCOMMENSURATE STRUCTURES
VVe will consider incommensurate structures that are described by displacement

modes of one IR n{ I<r,}v of the initial-phase space group G. The superscript // of
the IR will henceforth be omitted. The atomic displacement vectors connecting
the atomic positions in the initial phase and in the incommensurate phase may
be decomposed relative to the modes:
u(rin) = L 17L>.~(~LVI i)eil<Ltn, (41.2)

L>'
with rin = riO + tn, riO the position of the ith atom in the initial primitive
cell, tn the translation vector, L the number of the arm of the star {~L}
and .A the number of the basis function of the representation D{I<d v . In a
thermodynamic description of a phase transition to an incommensurate phase,
the mixing coefficients 1]L>. play the role of the OP's. The thermodynamic
potential has the following structure:
.1]-L>. +

L>'
+
LlJ···,L m
A,l"",A7n m~3
368 CHAPTER 10
The factor 8(""L 1 + ... + ""Lm) is a consequence of the translational invariance

of the potential in the initial phase and signifies that
m
L ""Lp = 0 (mod B), ( 41.4)

p=1
where B is the reciprocal-lattice vector. The orientational symmetry of the

initial phase places additional constraints on the coefficients u, leaving the
structure (41.3) unaltered. In addition to the habitual orientational and trans-
lational symmetry, the potential is invariant under the phase shift [26]:
(41.5)
if the following two conditions are satisfied, which place constraints on the
choice of the phases <PD.:
<PL>, = -<P-LA (mod z), (41.6)
L <PLpAp = 0
111
(mod z) (41.7)
p=1
(z being any integer). The first condition is associated with the quadratic
invariant in <1>, and the second condition is a consequence of the term 8(""L 1 +
... + t"L",) involved in equation (41.3). The conditions (41.6) and (41.7) should
be satisfied for all values of A. Therefore, the phase <PLA may be assumed to be
independent of the subscript A:
(41.8)
Allowing for equation (41.8), the condition (41.7) becomes

n
L <PLp = 0 (mod z). (41.9)
p=1
The number of phases <PL is related to the number of star {""L} arms.
A feature peculiar to incommensurate stars is that not all of the m arms are
independent. For example, the arms ""L and ""L+1 = -""L. Consequently,
d (d < m) independent arms J(p may be chosen. For the remaining d - m arms
of the star {""L} we may then write
d
""L = L nL"k".
,,=1
(41.10)
COLOR SYMlHETRY IN PHASE TRANSITION THEORY 369
Accordingly, we may isolate d independent phases "pu, in terms of which the

rest of the phases ¢ L may be expressed:
d
¢L = L:
u:1
nLu"pu. (41.11)
It is convenient to introduce the d-dimensional vectors

qL = 21l'(nLl,"" nLd),
(41.12)
tP = ("p1, ... ,,,pd)'
Thus the additional phase symmetry of the potential allows d-dimen-
sional color groups to be introduced for describing the symmetry of incom-
mensurate structures described by the IR D{"Llv of the crystallographic space
group. vVe shall represent elements of a d-dimensional color group as gin =
{hdThl + tn ItPln}, where hi is a crystallographic rotation element, Th, a non-
trivial translation and tn a translation. We call the crystallographic compo-
nents {hi Th , } and tn of an element 9ln base elements and the phases tP In color
elements or loads.
A further step is to determine the incommensurate-phase color groups
G D proper. As already noted, the structure of an incommensurate phase is
determined by a set of mode mixing coefficients 'f/L>' which, in turn, determine
the vector 1] in the OP space. Consequently, each direction of the vector 'f/ may
be associated with an appropriate incommensurate structure and vice versa.
Evidently, the symmetry group of the incommensurate structure should leave
the corresponding vector 1] invariant:
gln1] = 1], gin E GD ( 41.13)
The condition (41.13) gives a system of equations for determining the loads
tPln for each base element involved in the group GD.
The transformation law for the components of the vector 1] is determined
by the expressions (41.5), (41.11), and (41.12) and has the form
9ln'f/L>. = eiqLtPln L: D"L(hLI'ThL + tn)L>.,M~'f/M~' (41.14)

M~
where qLtPln = 21l'¢ln,L'

The expression (41.44) determines the multiplication rule for the elements
of the color group obtained:
( 41.15)
370 CHAPTER 10
The matrix R is determinable from the condition qL = qM R- 1. The vectors

qL and qM correspond to the arms "'L and "'M, which satisfy the condition
"'L = R""M, and are defined by the expression (41.12).
Now we find the phase loads for the translations gln = {h 1 It n l"pn}. The
expressions (41.13) and (41.14) yield
(41.16)
whence we have a system for finding the components of the vector "pn:
(41.17)
Using the condition (41.10) and allowing for the relation of the vectors ku and
tn to the primitive translation vectors aa and b a , we have
3 3
tn = ~ mnaaa , ku = ~Cuaba. (41.18)

a=l a=l
As a result, we obtain from equation (41.17) the expressions sought for the
components 1/Jnu:
3
1/Jnu = - ~ CU f3m nf3. (41.19)

f3=1
We wish to illustrate the use of the resulting expression (41.19) with the
example of the incommensurate structure described by the star {",6} of the
f.c.c. lattice. The arms of the star {",6} have the form
"'1,2 = ±j,t(b 1 + b 2 ) = ±(OOJl),
"'3,4 = ±Jl(b 2 + b 3 ) = ±(JlOO), (41.20)
"'5,6 = ±Jl(b 1 + b 3 ) = ±(OJlO).
Of the six arms, "'1 - "'6, three arms (d = 3) are independent ones:
( 41.21)
'Ve let all the six arms of the star {",6} participate in the formation of an
incommensurate structure. In this case the matrix nLu involved in equations
(41.10) and (41.11) has the form
1 0 0
-1 0 0
0 1 0
n= 0 -1 0
(41.22)
0 0 1
0 0 -1
The vectors qL involved in equation (41.17) are the rows of this matrix. Ac-
cording to the expressions (41.11) and (41.12), the same matrix determines the
vector 1/Jn" The representation (41.21) defines the matrix Cqf3:
(41.23)
while the matrix mna for the translations ai, a2, and a3 is
( 41.24)
From the expressions (41.19), (41.23) and (41.24), we find the form of the color
loads for the fundamental translations:
( 41.25)
Let the incommensurate structure now be described by the arms ~1 and

-~1 (d = 1). Then only the coefficients Cu = J-l and C 12 = J-l are defined; the
other coefficients, Cqf3 , are undefined. The translations ai, a2, and a3 have
the following loads:
( 41.26)
The form of the other elements can be found in a similar fashion. Thus we ob-
tain a color group for each incommensurate structure. Using the multiplication
rules (41.15), we can readily verify that the resulting set of elements generates
a group. Part of the base elements in this group may happen to be unloaded,
the rest of the elements have color loads. For example, the expressions (41.25)
tell us that for the three-arm structure all the three translations a", are loaded,
whereas in the case of the one-arm structure, as follows from the expressions
(41.26), we have only two loaded translations, al and a2. The elements that
remain unloaded are those that are involved in the symmetry group of the in-
commensurate structure when it is described in the language of space groups.
Thus, owing to the additional phase symmetry, it becomes possible to restore
the full (both orientational and translational) symmetry of incommensurate
structures. The restored translational symmetry resolves the paradox of 'the
Cheshire cat'.
372 CHAPTER 10
Restoring the orientational symmetry resolves the problem of the macro-

scopic symmetry of incommensurate structures. Recall that in the traditional
space-group description of incommensurate structures, the symmetry of these
structures reduced to the identity symmetry. This contradicted experimentally
observed macroscopic properties of incommensurate structures. Applying ad-
ditional phase symmetry permits us to restore all the spatial base elements,
the totality of which determines the macroscopic symmetry of incommensurate
structures [26].
42. Icosahedral Symmetry of Crystals. Quasicrystals
A NEW TYPE OF ATOMIC ORDERING

A major structural element in the description of crystal structures is the unit
cell, or the Bravais cell (see §7). N such cells oriented parallel to one another so
as to occupy densely the entire volume form a crystal lattice (Fig. 1O.1a). The
requirement that the entire volume be densely filled restricts the possible shape
of Bravais cells or, equivalently, their symmetry. The Bravais cell symmetry,
in turn, determines the orientational symmetry of the crystal. Thus a total
of fourteen Bravais cell types are possible; the symmetry of these cells may
contain only the rotations C 3 (30°), C 6 (60°), C 4 (90°) and C 2 (180°).
(a) (b)
Fig. 10.1. Examples of filling of the plane with rectangular (a) and
pentagonal (b) unit cells. The shaded area refers to 'voids' in the
filling of the plane with pentagons.
An icosahedral unit cell, which possesses a five-fold symmetry axis C 5

(72°), does not meet the requirement on dense occupation of the entire volume
(Fig. 10.1b). This fact implies that a crystal possessing simultaneously transla-
tional periodicity and an orientational five-fold symmetry cannot exist. That is
why the report [27] that the electron diffraction pattern of a rapidly quenched
Al86Mn14 alloy consists of spots whose symmetry contains five-fold axes along
with three-fold and two-fold axes (Fig. 10.2) has aroused great interest.
-- .---------~---,
0.·0····0··0
· · · , , · · o o . · g - •• g •••. g •• g· ••• o
Q' • • . II .•.•• I I · • • • II
II ••
. II .• •• "
.-
•• II
.
o· •• ·o ..
-
g·.··o
-
(a) (b) (c)
Fig. 10.2. Sections of the electron diffraction picture of the Al86Mn14

quasicrystal; with five-fold (a), three-fold (b), and two-fold (c) sym-
metry.
The presence of well-defined spots on the electron diffraction pattern indi-

cates the existence oflong-range order or a translational symmetry in AI86Mn14.
The symmetric arrangement of the spots points to the existence of an orien-
tational symmetry in the atomic arrangement. Specifically, this symmetric
spacing of the spots indicates the presence of five-fold symmetry axes which,
as noted above, is incompatible with translational periodicity. Thus the elec-
tron diffraction patterns presented in Fig. 10.2 constitute a crystallographic
paradox.
To resolve this paradox, it suffices to relinquish the assumption that the
alloy Al86Mn14 has ideal periodicity in the atomic arrangement and replace
the ideal periodic arrangement by a quasiperiodic arrangement. Crystals with
quasiperiodic atomic arrangement have come to be called quasicrystals [28].
In addition to A186Mn14' other representatives of quasicrystals are the alloys
Al74Si6Mn2o and Ah4Si6Mn22 [29].
Quasicrystals are produced during crystallization of a melt via·a first-order
phase transition when the melt is subjected to sufficiently rapid quenching. The
quasi crystalline state was shown [27] to be a sufficiently stable metastable state.
Thus heating the quasicrystal Al86Mn14 for six hours at 300 K and for one hour
at 350 K did not destroy the quasicrystalline state. Heating this quasicrystal
374 CHAPTER 10
during one hour at 400°C resulted in a transition to the usual crystal phase
A1 6 Mn 4.
THE GEOMETRIC ASPECT
As has already been stated, normal crystals may be viewed as a collection of

similar Bravais cells that densely occupy the bulk of the crystal. If the unit
cell has icosahedral symmetry, the dense-packing requirement is not fulfilled.
However, as shown by Penrose in 1974, a set of two dissimilar cells suffices
to ensure that the plane is densely filled [30]. The tilings that he obtained
(portrayed in Fig. 10.3) possess five-fold symmetry and may serve as a two-
dimensional model of a quasi crystal.
Fig. 10.3. Penrose tiling as a two-dimensional model of a quasicrystal.
Different Penrose cell shapes may be chosen. In Fig. 10.4 we show two
versions of choosing Penrose cells. Common features of these versions are the
values of the acute angles ¢ and obtuse angles 2¢, where ¢ = 27r/5. It is
precisely this value of the angle ¢ that is responsible for the five-fold symmetry
of Penrose tilings.
There are several algorithms for constructing Penrose tilings [30-33]. Of
these algorithms, the deflation method and the matching method are the easiest
to demonstrate.
The gist of the deflation method is that one of the rhombohedra (any
rhombohedron) is broken up into rhombohedra of the same shape but of smaller
(a) (b)
Fig. 10.4. Two different possibilities of choosing Penrose cells [28,30]:

obtuse and acute rhombi (a); kites and darts rhombi (b).
size. For example, let us take an obtuse rhombohedron (Fig. 10.5a), label one
of its vertices by the letter P l , and break it up into rhombohedra smaller in size,
as shown in Fig. 10.5b. We call the vertex PI the deflation pole. We choose
the vertices of the smaller rhombohedra that lie opposite the vertex PI as the
poles P2 oCthe next deflation (Fig. 10.5a). Then again, we choose the vertices
opposite to the vertices P2 as the deflation poles P3 and repeat the deflation.
As a result, we come to one of the versions of Penrose tilings (Fig. 10.3).
The matching method involves different ways of decorating Penrose cells
(tile shapes) and a set of matching rules that determine the algorithm of joining
the tile shapes together. One of the versions of decoration is presented in
Fig. 10.6a [34]. By joining the rhombohedra together in such a way that the
white and black arrows coincide, a tiling such as that shown in Fig. 1O.6b can
be generated. Another version of decoration and the tiling that corresponds to
it are shown in Fig. 10.6c, d.
The Penrose tiling (Fig. 10.3) possesses no translational periodicity. Put
another way, in Fig. 10.3 we cannot isolate a fragment and generate the entire
tiling by parallel translations of that fragment. The periodicity property in
Penrose structures is fulfilled approximately; that is to say, the Penrose tiling
is quasiperiodic.
To illustrate the notion of a quasiperiodic lattice, we mark the Penrose
376 CHAPTER 10
I
t--
(a) (b)
Fig. 10.5. Construction of Penrose tilings by the deflation method:

deflation poles P1, P2 , P3 (a) and deflation algorithm (b). The double
line represents the initial rhombus. The dashed line refers to the first
deflation; the solid line refers to the second deflation.
tiles as shown in Fig. 10.7 [32]. A set of five parallel grid lines will then appear
on the tiling assembled from these cells. As can be seen, the spacing of lines in
each set is close to periodic. The separation between adjacent planes is
(42.1)
where
1 n
Xn = n+ -l-
T T
+ Cd + C 2• (42.2)
Here n is the plane number; T = HI

+ .;5) is an irrational number, often
called the golden ratio; C 1 and C 2 are arbitrary numbers. The symbol LxJ
represents the greatest integer that does not exceed the value of x. The first
()
A o
Fig. 10.6. Examples of decorating Penrose cells and the corresponding
tilings.
v,
/\
" ',,:
,
(a) (b)
Fig. 10.7. Decoration of Penrose tilings (a) and cells (b). An illustra-
tion of the quasiperiodicity property of a 2-dimensional quasicrystal.
term in equation (42.2) describes a periodic spacing of planes, and the second
term gives a quasiperiodic addition. The spacing of the planes described by
the expression (42.2) is characterized by two interplanar spacings dL and ds
and it is easy to see that dLlds = 1 + liT. The presence of two interplanar
distances distinguishes a quasiperiodic spacing of planes from periodic and
378 CHAPTER 10
incommensurate spacings. An incommensurate spacing may be viewed as a

superposition of two periodic sets of planes with incommensurate periods. In
the incommensurate structure thus obtained, adjacent planes may be spaced
as close to each other as desired.
The points of intersection of five sets of quasiperiodic parallel planes gen-
erate a quasiperiodic lattice. If we describe such a lattice by a set of delta
functions associated with quasiperiodic-lattice sites, then the Fourier series ex-
pansion of such a function will contain a finite number of harmonics [34,35]. In
other words, the diffraction pattern of such a quasiperiodic lattice will consist
of Bragg reflections numbered by a finite set of wave-vectors. Thus, although
possessing no periodic lattice, the Penrose tiling is nevertheless characterized
by diffraction patterns similar to those for the usual crystals. This feature of
structures such as Penrose tilings accounts for the use of the terms 'quasicrystal'
and 'quasiperiodic lattice'.
The number of sets of parallel lines and their relative orientation are im-
portant characteristics of quasiperiodic structures as each structure may be
associated with its own wave-vector star {"'L}. Each arm "'L of such a star is
perpendicular to the planes of one of the sets. The length of each arm is deter-
mined by the spacings d L and d s between adjacent planes of the corresponding
set:
1 n
X"'L = XLn = n + - L- + ClLJ + C2L
T T
(42.3)
The Penrose tiling depicted in Fig. 10.3 corresponds to a five-arm star with
arms of equal length (Fig. 10.8).
Fig. 10.S. Wave-vector star for the Penrose tiling.
Thus every quasiperiodic structure may be placed in correspondence with

its own wave-vector star. Such correspondence underlies the algorithm of con-
structing quasiperiodic structures. This algorithm is known as the lattice
method [33].
Apart from the lattice method, one employs also the projection method
[36], which is equivalent to the lattice method [37]. The gist of the projection
method is that a quasi crystalline structure may be viewed as a mapping of a
multidimensional structure, periodic in multidimensional space, onto a space
of lower dimension. For example, a one-dimensional quasiperiodic lattice may
be viewed as the projection of a strip of a two-dimensional periodic lattice,
indicated by a dashed line in Fig. 10.9, onto the AB line.
B
/
;L
\«
'<
'0.':
" /
/
/
/
V /
/ /
/
V,
/
/
JI. /
/ /
/
Fig. 10.9. One-dimensional quasiperiodic lattice as a result of pro-

jecting a two-dimensional periodic lattice.
With reference to an example of Penrose tilings we have considered the

major geometric properties of two-dimensional quasi crystal lattices. We may
similarly investigate geometric properties of three-dimensional quasiperiodic
structures [28,31-34]. Just as in the two-dimensional case, three-dimensional
quasiperiodic structures may be constructed from two three-dimensional unit
cells such as those sketched in Fig. 10.10 [28].
THE THERMODYNAMIC ASPECT
The quasicrystal phase in AI86Mn14, as stated above, forms from the melt as
a result of a first-order phase transition. To describe such transitions thermo-
dynamically, we may exploit the Landau theory, the major principles of which
are outlined in Chapter 1. All the distinctions of the crystallization-type tran-
sition under consideration from the crystal-crystal transitions treated in the
preceding chapters will tell on the definition of concepts such as the initial or
380 CHAPTER 10
(Oll)o.
(o-n)a
(70-1)Q
(C, L)
Fig. 10.10. Three-dimensional unit cells for constructing three-dimen-
sional quasiperiodic structures.
high-symmetry phase, low-symmetry phase, order parameter, and thermody-

namic potential.
For AIs6Mn14 the initial phase is represented by a liquid phase plus a melt
and its symmetry is described by the group Go = 0(3) x T, where 0(3) is the
rotation group and T is the continuous translation group. By low-symmetry
phases, in addition to the usual crystalline states of different symmetry, we
will understand also liquid-crystalline and quasicrystalline states. As usual, we
will assume that the structure of the initial phase is described by the density
function po(r), which does not vary when we act on it with elements ofthe group
Go. The variation of the density function ~p( r) = p( r) - Po( r) describes the
phase transition to the low-symmetry phase. The function ~p(r) is invariant
under the symmetry group of the low-symmetry phase.
vVe choose the density function in the form
~p(r) = l: r/Lei"Lr, (42.4)

"L
where the "'L are the star {K,L} arms numbering the IR's of the group Go. The
expression (42.4) for the density function ~p(r) is a model choice. This choice
can readily be understood in terms of group theory. By choosing the density
function in the form (42.4), we allow for part of the IR of the group Go. That
is, of all the possible IR's of the group Go that may participate in the forma-
tion of incommensurate phases, we consider the IR's of the translation group
only. In other words, rather than considering all the low-symmetry phases
possible, we restrict our attention to those that are described by a transla-
tional OP. The orientational symmetry in these phases is a consequence of the
translational symmetry. Phases that are characterized only by orientational
symmetry without long-range order are not considered in such an approach. In
the following, however, we restrict ourselves to the choice of the density func-
tion /1p in the form (42.4) since this function describes the main properties of
quasicrystals.
The thermodynamic potential invariant under the group Go has the form
 = r L 'fJL'fJ-L + V3 L 'fJL'fJM'fJNb("'L + "'M + "'N)+

L L,N,M
+Ul L('fJL'fJ-L)2 + U2 L 'fJL'fJ-L'fJM'fJ-M+

L LM
+V5 L 'fJL'fJM'fJN'fJP'fJSb("'L + "'M + "'N + "'p + "'S) + .... (42.5)

LMNPS
Here we have not written out the sextic invariants whose coefficients are as-
sumed to be positive. The signs of the coefficients V3 and V5 may be both pos-
itive and negative. The potential (42.5) is written on the assumption that the
phase transition is described by one IR whose index is omitted. The potential
(42.5) does not depend on the direction of the wave-vector "'L (a consequence
of its invariance under the rotation group 0(3)) and depends sensIbly on the
relative position of these vectors. Examples of the various stars, differing in
the relative position of the arms "'L, are given in Fig. 10.11.
4!f
/~-
... \
\
\
-
Fig. 10.11. Examples of wave-vector star describing different types of
structure.
Figure 10.11a shows three arms of a coplanar six-arm star {"'t}, which
satisfy the condition "'L + "'M + "'N = O. The unshown three arms are opposite
382 CHAPTER 10
to the arms K.1, K.2, and K.3. In Fig. 10.llb we present five arms of a coplanar
=
ten-arm star {K.p }, which satisfy the condition K.L + K.M + K.N + K.p + K.s O.
The coplanar structure described by this star is a two-dimensional quasicrystal.
Penrose tilings may serve as a model of such a structure. Indeed, the star {K.p }
coincides with the star shown in Fig. 10.8 which underlies the construction of
tilings in the lattice method.
The non-coplanar twelve-arm star {K.o}, whose arms generate an octahe-
dron (Fig. 1O.llc), describes crystal structures with a b.c.c. lattice [39]. Two
non-coplanar stars, {K.Il and {K.j}, are related to the icosahedron portrayed in
Fig. 10.lld. Thirty arms of the star {K.Il generate the edges ofthe icosahedron
(Fig. 10.11 d). The twelve-arm star {K./} is related to the vectors directed from
the center of the icosahedron to its vertices. Both stars {K.J} and {K.j} are
responsible for the formation of quasicrystalline phases [38,40].
We pass over to the new variables
(42.6)
and minimize the potential (42.5) with respect to the angles OL. Only the terms
V3 and V5 depend on the variables OL in the potential (42.5). On substituting
equation (42.6) into equation (42.5), these terms become
(42.7)
The symbols ~ and <> here denote sUmrilation over the arms satisfying the
= =
conditions K.L + K.M + K.N 0 and K.L + K.M + K.p + K. n + "'5 0 respectively.
In principle, the quartic and sextic summands in the potential ~ include terms
that depend on the angles OL, but we neglect these terms.
We assume that the coefficients V3 and V5 are positive. Then the condi-
tions for the potential ~ to be minimal are satisfied by the following values
of OL: OL = (2n + 1)11' (n= 0,1,2, ... ). Substitution of these values into the
expressions (42.7) yields
(42.8)
These expressions tell us that in the quartic model the lowest energy belongs to
a b.c.c. crystal phase, whose formation is described by the star {K.o} [13]. The
energetic favorableness of the quasicrystalline phase described by the star {K. I}
may be achieved only in the sextic model, owing to the term V5 [38,39]. Similar
lines of argument show [41] that the quasicrystalline phase may nevertheless
prove to be energetically favorable in the quartic model if one includes into the
consideration two 0 P's {1Jd and {ed corresponding to the stars {K. I} and
{K.~ }.
An analysis of the theoretical diffraction picture for a quasicrystalline
structure described by the 'edge' star has shown [42,43] that for such a struc-
ture the X-ray pattern section perpendicular to the two-fold symmetry axis
does not coincide with experiment on AI86Mn14. In the corresponding section,
experimental diffraction patterns contain reflections that do not arise in the
edge model. Therefore a model [41] with a potential of the form
15 6 30
(J) = r1 L 1JL1J-L + r2 L eLe-L + V3 [ L 17L1JM1JN8(K.L + K.M + K.N)+

L+1 L=l L,M,N=l
30 12
+ L L 1JLfMeN 8(K.L + qM + qN)] +

L=l n,lI!=l
30
+u[ L
L,M,N,P=l
12
+ L eLeMeNe p 8( qL + qM + qN + qp)+
L,M,N,P=l
30 12
+ L L 1JL1JMeNe p 8(K.L + K.M + K.N + K.p)] (42.9)
L,M=l N,P=l
may be regarded as the most probable one for describing the quasi crystalline
state of A186Mn14. In the expression (42.9) the symbols K.L and qL denote the
384 CIIAPTER10
arms of the stars {K.Jl and {K.~} respectively. In deriving the potential (42.9),
the following assumptions have been used.
(1) The density function components TJL and eL corresponding to the 'edge'
K.L and 'vertex' qL arms of the stars {K./} and {K.~} are equal partners par-
ticipating in the formation of the quasicrystalline structure in AIs6Mn14' The
necessity of simultaneously allowing for the parameters {TJL} and {eL} was first
noted in [40] in connection with the fact that the arm moduli IK.L I and IqL I
differ by as small an amount as 5%.
(2) The coefficients of the third-degree invariants are equal in magnitude.
The same applies to the coefficients of the quartic invariants, in which case
u > O. Such an approximation implies that we neglect the anisotropy in higher-
order invariants.
= =
We write TJL TJe i9L and eL ee ih and restrict our attention to the most
symmetric quasicrystalline phase (1£ = cPL = O. The potential (42.9) may then
be rewritten in the form
(42.10)
The {j functions contained in the potential (42.9) determine the number of the
=
corresponding terms, giving the values of the coefficients v 0.23 and w 4.39. =
1
i
(zo)
1<-- (00 )
't.z
-+------~ .... - - - - -
Fig. 10.12. Phase diagram in the mogel (42.10). K, critical point.
Analysis of the thermodynamic potential (42.10) leads to the phase dia-

gram shown in Fig. 10.12. The model under consideration describes the pos-
sibility of the formation of two quasicrystal structure types: a 'vertex' qua-
sicrystal structure, corresponding to the phase ("10), and a 'mixed' structure,
corresponding to the phase ("Ie). The ("Ie) phase may form both by a first-order
transition and by a second-order transition. The phase transition between the

phases (7]0) and (7]e) may be of both first and second order. The (7]0) +-+ (7]e)
phase transition line has a critical point J{. Therefore, as follows from the
model proposed in [41], a 'mixed' quasicrystalline structure described by two
stars {'"Il and {"'~} at once should arise for certain ratios of the coefficients
T1 and T2. In this model the formation of the 'edge' structure (Oe) which, as
stated above, does not describe experimental diffraction patterns, is forbidden

by the invariant 7]e.
Problems of X-ray diffraction on various crystal structure types differing
in the way the stars {"'I} and {"'~} participate in their formation are treated
in [28,34,42,43].
THE SYMMETRY OF QUASICRYSTAL STRUCTURES
As already noted, the structure of the quasicrystalline phase is defined by par-

ticular values of the angles 8L. Indeed, in the one-harmonic approximation,
at the transition over the coplanar star {",p}, the quasicrystal structure cor-
responding to the values 8 = 7r /2 is described by a density function of the
form
5
Llp1(r) =L 7]sin("'Lr). (42.11)
L=l
At 8 = 0,7r the density function describing the structure of the quasicrystal

has the form
5
Llp2(r) = L 7] cos("'Lr). (42.12)
L=l
The structure described by the function Llp2(r) is shown in Fig. 10.13, which
has been obtained by superposition of five plane waves propagating along the
arms of the star {"'p}. A peak of each wave is indicated by a solid line. The
places where the density function Llp2(r) is at a maximum are marked with
dots.
It is readily verified that the quasicrystal structures described by the func-
tions LlP1 and LlP2 are different from each other. Thus the structure Llp2(r)
is symmetric under the replacement r -+ -r, whereas the structure LlP1 (r)
possesses no such symmetry element.
The symmetry of the quasi crystal structure can be determined in the
usual way, by picking out those elements of the initial-phase symmetry group
Go that leave the corresponding density function invariant. For example, the
quasicrystal structure described by the density function (42.11) possesses no
386 CHAPTER 10
Fig. 10.13. Quasiperiodic structure obtained by superposition of five

plane waves (42.12).
translational symmetry. The point group of this structure consists of rotation

elements C5 .
In this approach to the determination of the symmetry of quasicrystals,
just as with incommensurate structures, part of the symmetry elements are
lost. Thus the structure described by the density function (42.12) is invariant
under the replacement (h ...... BL + 27r, which may be viewed as translations in
the phase space. Consequently, the symmetry of quasicrystal structures may be
described by multidimensional color groups, by analogy with the description
of incommensurate structures (see §41). The meaning of multidimensional
color groups becomes apparent if we regard quasicrystal structures as resulting
from the projection of multidimensional periodic structures on Cartesian three-
dimensional space.
Consider the quasi crystal structure described by the twelve-arm star {"'~}
and the set of phases 4> L = 0 obtained from the condition that the potential
be minimal. Of the twelve star {"'/} arms corresponding to the vertices of the
icosahedron (Fig. 10.11), only six arms are independent; the other six arms
differ in sign. The density function
6
~p(r) = EeL cos(K.Lr + tPL) (42.13)
L=1
is invariant under the six translations tPL -+ tPL + 271". We will treat the six
phases tPL as the unit vectors of six-dimensional space. The condition tPL = 0
assigns a point in this space, and the translations tPL -+ tPL + 271" generate
from this point a six-dimensional lattice, which may be called a simple six-
dimensional cubic lattice [38].
Let the quasicrystal phase be described by the thirty-arm star {K./}, whose
arms are parallel to the edges of the icosahedron. Inspection of Fig. 10.11 shows
that each edge of the icosahedron (each arm of the star {K.~}) may be viewed
as a sum of two vectors directed from the center to the vertices (two arms of
the star {K.~}): K.L = qM - qN. The density function may be written in the
form
15 6
~p(r) = E 'TIL cos(K.Lr + OL) = E 'TIM-N cos [(qM - qN)r+ (tPM - tPN)].
L=1 M,N=1
(42.14)
Just as in the foregoing, we may assume that the six tPL phases are unit vectors
of six-dimensional space. The values (h = 0,71" minimizing the potential with
respect to the values of V3 and V5 assign a point in this space. The translations
that generate the lattice consist of the translations tPL -+ tPL + 271" and an extra
translation tP1 -+ tP2 + 71", tP2 -+ tP2 + 71", ... , tP6 -+ tP6 + 71". The resulting set of
translations generates a six-dimensional body-centered cubic lattice [38].
Thus the quasicrystal structures described by the stars {K.J} and {~~}
differ from each other in the same way as, for example, cubic crystals with
b.c.c. and s.c. lattices do. The symmetry groups of the corresponding phases
have identical zero blocks (see §12) and different sets of six-dimensional trans-
lations. In both structures the zero block consists of twelve elements C 5 , twelve
elements Cg, twenty elements C3 , and fifteen elements C2 [38]. Knowledge of
the quasicrystal's symmetry group is needed in investigating elastic properties
of crystals [38], elastic oscillation spectra [44], and a number of other problems.
AI/36Mn14: A FIBONACCI STRUCTURE OR A QUASICRYSTAL?
The discovery of quasicrystals was stimulated by crystal structure investiga-

tions of AI/36Mn14 alloys. Somewhat later a counterversion [45] was advanced
388 CHAPTER 10
leading to separation of a new crystal structure type, called Fibonacci struc-

tures. According to that version, Al86Mnl4 alloys are cubic-symmetry crystals.
A feature peculiar to these crystals is that they have a large unit cell with an
edge a rv 33 A. Such a version is capable of explaining also the unusual diffrac-
tion pictures of these alloys. Indeed, let us compare the wave-vectors corre-
sponding to the reflections observed in the cubic model with those observed in
the quasi crystal model. Assume that the quasicrystal model corresponds to the
star {ti~} [38,40]. The arms of the star {ti~} may be written as a superposition
of 'vertex' arms such as (ITO), (0 1 T), etc., where T is the golden ratio. In
the cubic model the notation of the observed reflections is (3, 5, 0); (5, 8, 0);
(8, 13,0); etc. The direction of the vectors (3, 5, 0) and (1 T 0) differs by 1%,
that of (5, 8, 0) and (1 T 0) differs by 0.5%, and that of (8, 13, 0) and (1 T 0)
by 0.2% [45]. This closeness of the vectors in the quasicrystal and cubic models
determines two alternative ways of deciphering the structure of Al86Mnl4' If
we choose the reflection (8, 13, 0) as the fundamental (progenitor) reflection
determining the cubic unit cell size d, we obtain d = 33.09 A.
The cubic model proposed in [45] possesses the following remarkable pe-
culiarity. In this model, most of the reflections observed may be written as
(0, 0, 2a n ); (0, an, an+I); (an+l' an, an-I), where the an are the Fibonacci
numbers: an = 1,2,3,5,8,13,21 [46]. The following recurrence relation holds
for the Fibonacci numbers: an+l = an + an-l' Therefore, the corresponding
wave-vectors that participate in the formation of such a cubic structure satisfy
the equation tiL+l + tiL + tiL-l = O. This condition reveals the role of the
cubic invariants (involved in the thermodynamic potential), which may be re-
sponsible for the energetic favorableness of such structures as compared with
structures corresponding to other wave-vectors.
Thus the presence of cubic invariants in the thermodynamic potential iso-
lates, from among all the possible wave-vectors, vectors of the type (0, 0, 2a n );
(0, an, an+d; (a n+1. an, an-d, where the an are the Fibonacci numbers.
Since cubic wave-vectors are close to icosahedral ones, the geometric properties
of such structures are close as well. Consequently, the interference pictures, too,
are close. The authors of [45] suggest calling such cubic structures Fibonacci
structures. Further investigation of their properties is of great interest.
CONCLUSION
The results of describing quasicrystals on the basis of Landau's thermody-

namic theory may be summarized as follows. One of the major consequences
of Landau's theory is the conclusion that over a certain temperature interval

the quasicrystalline state may have a lower energy as compared with the usual
crystalline state with a b.c.c. structure [39,46]. This conclusion has been ob-
tained in the sextic-OP model [38] and in the quartic model with two coupling
OP's [41].
The icosahedral-symmetry quasicrystal structures thus obtained are the
simplest representatives of non-crystallographic-symmetry quasicrystals. It is
clear that allowance for higher degrees in the expansion of the thermodynamic
potential permits us to find energetic-favorableness conditions for quasicrys-
tals with a different symmetry (for example, the seven-fold symmetry due to
allowance for seventh- and eighth-order terms in the potential). In practice,
however, the formation of such quasicrystals, just as the formation of low-
symmetry phases at normal phase transitions such as crystal-crystal transitions,
calls for more stringent constraints on the coefficients of the thermodynamic
potential, thereby substantially lowering the probability of the realization of
quasicrystals.
A remarkable fact is the possibility of describing quasicrystal structures in
terms of a multicomponent OP specified by an appropriate wave-vector star and
a set of its arms, in complete analogy with crystal-crystal phase transitions. An
important point is that quasicrystal structures are multi-~-structures, since all
arms of the corresponding star participate in the formation of these structures.
In normal phase transitions in crystals, most of the structures are described by
one wave-vector star.
Interpreting quasicrystal structures as multi-~-structures permits resolu-
tion of the seeming crystallographic paradox residing in the simultaneous man-
ifestation of a non-crystallographic five-fold symmetry incompatible with the
three-dimensional periodicity of the crystal lattice or, equivalently, with the
occurrence of well-defined Bragg reflections that indicate the presence of a
translational symmetry. This paradox is easy to resolve when it becomes clear
that quasicrystal structures may be obtained by superposition of 2n + 1 plane
waves. Their relative position ensures a (2n + I)-fold rotational symmetry in
real space, and the corresponding wave-vectors determine the position of Bragg
reflections in reciprocal space.
Finally, the possibility of describing quasicrystal structures within the
framework of the Landau theory with the use of such concepts as the initial
phase, thermodynamic potential, and order parameter enables one to investi-
gate the effect of external fields on the formation of quasi crystals and on their
390 CHAPTER 10
equilibrium properties, and also to explore their dynamic properties near the
ground state [38,48].
A different outlook on quasicrystals as structures corresponding to chaotic
solutions of some non-linear equations is given in [49].
43. Color Groups in the Theory of Systems with a

Quantum Mechanical Order Parameter
THE QUANTUM MECHANICAL ORDER PARAMETER
By the definition of the OP, one should choose as the OP a quantity that is
equal to zero in the initial phase and is non-zero in the low-symmetry phase.
In the case of a superconducting phase transition this quantity is a function of
the form
(43.1 )
which has the meaning of the wave-function of a Cooper pair (see, for example,
[50,51]). Here", is the wave-vector of an electron, Q' and j3 are the spin variables
of an electron and C,WI the Fermi annihilation operators of an electron in the
state "'Q'.
The OP's that we treated in all the previous sections were classical quanti-
ties such as displacements of atoms from equilibrium position, atomic magnetic
moments, the probability of finding an atom of a given species in a given site,
etc. In the case of a super conducting phase transition we encounter for the first
time an OP that is of a quantum-mechanical nature. The new level of describing
the phase transition manifests itself primarily in the determination of the sym-
metry group of the initial normal phase. Indeed, the wave-function describing a
particular state of the system is given to within a phase factor. A consequence
of such indeterminacy is the invariance of the Ginzburg-Landau functional un-
der the gauge transformation group U, whose elements describe the phase shift
of the quantum-mechanical OP [51]. Apart from this, the Ginzburg-Landau
functional should be invariant under the transformations of the crystal point
group Go and under the time-reversal operation R. In the strong-spin-orbit-
coupling approximation the full group G of the initial phase may therefore be
represented as G = Go x R x U. The group G and its subgroups GD are color
groups. The necessity of employing color groups to describe ordered phases
was noted by Volovik and Gor'kov [52]. In the following we will base ourselves
chiefly on the results obtained by these authors.
Consider the symmetry of the OP ~O',6 (~) with respect to the substitutions
~ -+ -~ and a -+ (3. We single out two cases, which correspond to the total
spin S = 0 and S = 1, and write the expression (43.1) in matrix form [53]:
S = 0: Lio(~) = 'ljJ(~)i(Ty,
(43.2)
S = 1: Lil(~) = ((Td(~))i(Ty,
where the (TO' are Pauli matrices. The quantity ~o(~) stands for the usual
Cooper pairing of electrons with opposite spins. The parameter ~1 (~) de-
scribes the triplet pairing of electrons with parallel spins. Problems of non-
trivial superconductivity with triplet pairing as well as possible realization of
such superconductivity are discussed in [54,55]. It follows from the definition
of the OP (43.1) that
( 43.3)
For S = 0 and S = 1 the condition (43.3) takes the form

S = 0: 'ljJ(~) = 'ljJ(-~),
( 43.4)
S = 1: d(~) = -d(-~).
Thus the scalar function 'ljJ(~) is even with respect to the replacement ~ -+ -~,
while the vector function d(~) is odd.
CLASSIFICATION OF ORDERED PHASES ON THE BASIS OF COLOR SUB-GROUPS

OF THE NORMAL-PHASE SYMMETRY GROUP
Superconducting phase transitions belong to group-subgroup related transi-

tions. This means that the symmetry group of the low-symmetry phase G D
must be a subgroup of the symmetry group of the initial phase G = Go x R xU.
Thus the search for all the possible superconducting phases in a given crystal
may be reduced to enumerating all the subgroups GD of the group G. vVe
will represent elements of the group G as g = {h IRlq\}, where h is an element
of the point group Go, and q\ signifies that the action of an element h on the
OP is accompanied by a phase shift as a fact?r exp(iq\). Elements of the form
g = {hIOIO} will be called non-loaded elements or base elements. Elements of
the form g = {hIRIq\} will be called either loaded or color elements.
It is appropriate to note an analogy between the group under consideration
G = Go x R x U and the exchange group of the paramagnetic phase P =
G X l' x 0+(3) in the theory of magnetic structures (see §40). Here G is the
space group of the crystal, l' is the spin inversion operation and 0+(3) is the
392 CHAPTER 10
spin rotation group, which does not affect the atomic coordinates. Elements
of the group G act only in coordinate space. The problem of enumerating the
magnetic subgroups Mp of the group P is treated in detail in [7,56,57]' and in
the following we use some recipes of these papers to find the superconducting
color groups G D.
All the possible groups G D may be subdivided into two types according
to the way the element R is combined with the base elements. The subgroups
of the first type have the structure GD! = H x R, where H either coincides
with the group Go or is a subgroup of it. We will call ordered phases that
are described by groups of this type usual superconductors [53]. The groups
GD! involve a time reversal in the form g = {hlIRIO} (h l being an identity
element), so the corresponding phases are non-magnetic. The enumeration of
the subgroups of the first type is a trivial one and reduces to the subgroups of
the crystallographic point groups.
The subgroups of the second type G D2 contain combined elements, that
is, along with non-loaded elements g = {hIOIO}, the group GD2 contains color
elements of the form g = {hIRI¢}. According to whether or not the element R
is involved in the group G D2, the non-trivial superconducting phase may either
possess or not possess magnetic properties. In the case of magnetic structures,
the color exchange groups Alp are analogs of the groups G D2. We will make use
of this analogy in enumerating the various GD2 type subgroups by the example
of cubic crystals Go = Oh.
To begin with, consider the action of the non-loaded inversion g25 =
(h 25 1010) on the functions 1j; and d. From the evenness of the function 1j;(K,)
and the oddness of the vector function d(K,) with respect to the substitution
K, ---+ -K, (see equation (43.41)), it follows that
g251j;(K,) = 1j;(K,),
(43.5)
g25d(K,) = -d(K,).
It then follows from the requirement of invariance of the OP Li under the sym-
metry group G D2 that in the case of singlet superconductivity (S =
0) the
inversion involved in the group G D2 is non-loaded, while for triplet supercon-
ductivity (S = 1) the inversion involved has a load ei7r , that is, has the form
g25 = (h Z5 1017T) or g25 = (h 25 IRI7T). This conclusion holds good for all groups of
the second type G DZ. In enumerating these groups in the case of cubic crystals,
we may therefore restrict ourselves to the group Go = 0 (Oh = 0 x T) instead
of the initial-phase group Go = Oh. The inversion may be added at the final
stage, allowing for the peculiarities noted in the cases S = 0 and S = 1.
There are several methods of enumerating color groups (see, for example,
[56,57]). One of them rests on the isomorphism theorem [58] according to which
any color group GD must be isomorphic to a space group. The formulation of
the theorem contains an algorithm of finding color loads for base elements of
the space groups. According to this algorithm, to find groups G D2 isomorphic
to the group Go, a normal subgroup H should be isolated in the group Go.
Then the group may be decomposed into cosets:
(43.6)
Each coset may be viewed as an element Ii of the factor group F:
F = Gol H = (ft, 12,··· .In). (43.7)
Take the group P = (pi, ... , Pn), whose elements are elements of the color
loads. If the group P is isomorphic to the group F, then by the theorem [58],
a color load Pi may be assigned to all elements of the coset Ii = gi H. As a
result, we obtain a color group GD2 isomorphic to the group Go.
For example, letting H =
T, the group Go =
0 may be decomposed into
cosets:
(43.8)
The factor group F = OIT is isomorphic to the group C2. Next, from the
elements of the groups U and R we may construct the group P = (1, ei1f )
isomorphic to the factor group C2 • Then the color group sought, Gm = O(T),
must have the form
(43.9)
Inasmuch as the element R is not involved in the group P, the final result for
the group GD2 may be represented as GD2 O(T) x R. =
In addition to the group T, we may choose as the normal subgroup of the
group 0 also the group D 2 • Then we have the following decomposition of the
group 0 into cosets relative to the subgroup D 2 :
(43.10)
The factor group F = OlD 2 is isomorphic to the group D 3 • The load group P
may be chosen in the form
21ri
P = (1, f.2, f., Rf. 2 , R, Rf.), where f. = exp ("3)'
394 CHAPTER 10
The corresponding color group C D2 isomorphic to the group consists of the

elements
C D2 = 0(D2) = D2 + {h510If2}D2 + {h 910k}D2+

+{h14IRk 2}D2 + {h19IRI0}D2 + {h24IRk}D2. (43.11)
The groups T and D2 exhaust the list of normal subgroups of the group 0, so
the rest of the groups C D2 will be isomorphic to the subgroups of the group
o : T, D4, D 3 , C3 , D 2, and C2. In finding the rest of the groups C D2
we proceed similarly, considering the normal subgroups of each of the groups
enumerated.
We construct color groups CD2 isomorphic to the group T. As the normal
subgroup we may take the group D 2. The factor group F = T / D2 is isomorphic
to the group C3 . The corresponding group of loads has the form P = (1, f, (2).
As a result, we obtain the required color group CD2 = D2 + {h 510If2}D2 +
{h 910k 2JD 2. Note that this group could be obtained as a subgroup of the
color group CD2 = O(T) x R already found. By exhausting the rest of the
possibilities, we obtain a complete list of color groups of the second type. The
maximal groups in this list have the form:
O(T) x R = [T + {h131017r}] x R,
0(D2) = D2 + {h510If2}D2 + {h 9 10If}D2 + {h14IRk 2}D2+
+{h19IRI0}D2 + {h24IRjf2}D2'
D 4 (CI) = C1 + {h41017r}C1 + {h1410IHC1 + {h15 101- t}C1+
+{h2IRI7r}C1 + {h3IRI0}C1 + {hdRlt}C1 + {h16IRI- t}C1, (43.12)
D4(C4) x R = [C4 + {h21017r}C4] x R,
D4(D~) x R = [D~ + {h141017r}D~] x R

R being the time reversal group R = {I, I'}. The groups D2 and D~ differ
in the direction of the two-fold axes in the xy plane. In the group D2 these
axes are parallel to the cube edges, in the group D~ they are parallel to the
bisectors. The rest of the color groups CD2 are subgroups of the maximal
groups (43.12). For example, the groups D4(D 2) x R = [D2+{h141017r}D2] x R
and D 3 (C3 ) x R = [C3+{h141017r }C3 ] x R are subgroups of the group O(T) x R.
OP SYMMETRY AND THE BEHAVIOR OF THE GAP IN K, SPACE
Enumeration of the color groups of possible ordered phases is an auxiliary stage

of the thermodynamic theory of phase transitions. Now we need to place each
group GD in correspondence with an appropriate OP and to specify the IR

that determines the transformation properties of that OP and the form of the
thermodynamic potential.
The conventional method of deriving such information is to use the explicit
form of the initial-phase symmetry group G. For each group GD we find by
the Birman criterion (see §8) the corresponding IR and the mode mixing coef-
ficients, or the type of solution of the equations of state. For superconducting
=
phase transitions the symmetry group of the initial phase is G Go x R xU.
Tables similar to those for space group IR's are not available for such groups,
so special efforts are required in each particular case in order to compute them.
In practice it is therefore convenient to try to relate the phase transition into
a particular GD phase to representations of the crystallographic group Go, as
was done in §41 when analyzing incommensurate structures.
In our case the group Go = 0 has five IR's: Tl(A 1 ), T2(A 2), T3(E), T4(Fd,
and T5(F2)' The representations Al and A2 are one-dimensional, the repre-
sentation E is two-dimensional and the representations Fl and F2 are three-
dimensional. Consider the representation A 2 • For the cases S = 0 and S = 1
the basis functions transforming according to this IR may be chosen in the
form [53]:
(43.13)
(43.14)
The expressions (43.13) are easy to obtain by the projection operator method
or the invariants method (see §21). The function f(K.) is invariant under the
group Go = O. Evidently, the functions (43.13) and (43.14) are invariant under
the group G D = O(T) x R. Indeed, since what corresponds to the elements
hl - h12 in the representation A2 is the identity matrix 1, these elements as
part of the group GD should have no loads, that is, they should be of the form
g = {hiOiO}. The rest of the group 0 elements h 13 - h24 in the representation
A2 correspond to the matrix -1. In pure form without loads, these elements
do not leave the functions tf;( K.) and d( K.) invariant and may not be part of
the group G D. The minus sign may be compensated for by the color load
e i 1l"; as a result, the elements corresponding to the matrix -1 of the IR A2
are introduced into the group GD • Since the functions (41.13) and (41.14) are
real, each of the group O(T) elements may be taken in combination with the
element R. The final result is that the representation A2 corresponds to the
group G D = O(T) x R.
396 CHAPTER 10
The explicit form of the expressions for 7I"(K.) (43.13) and d(K.) (43.14)
defines the directions (on the Fermi surface) in which the conditions
(43.15)
and
(43.16)
are satisfied. Fulfillment of these conditions isolates on the Fermi surface the
symmetry-induced points and lines corresponding to the zero gap in the Fermi
excitation spectrum [53,59]. The expression (43.13) says that in the singlet
phase (S = 0) described by the representation A 2 , symmetry-induced zeros
in the gap appear at the intercept of the Fermi surface with planes such as
K.II [110]. In the triplet phase (S = 1), as can be seeen from equation (43.14),
the condition (43.16) is fulfilled at the intercept of the Fermi surface with the
cube edges K.II [100] and body diagonals K.II [111].
The occurrence of zeros in the OP excitation spectrum is due to the pres-
ence of color elements in the symmetry group of the ordered phase. This can
be readily verified if, with a specially chosen direction of the vector K., we act
with these elements on the OP. Thus for S = =
1, the element gI6 {h I6 1017l"} is
a loaded element, where h I6 is a rotation by 180 0 about the xii axis. Choose K.
parallel to the [111] axis: K.O = /\:(111). Act on the vector d(K.o) with the ele-
ment g5 = {h 5 1010} involved in the group GD = O(T) x R. From the invariance
condition g5d(K.0) = d(K.o), it follows that the vector d(K.o) should be parallel
to the [111] axis: d(I>.o) II [111]. Then we have d(K.o) =
{h I6 1017l"}d(K.o)=
-h16d(hI61>.0) = -hI6d( -1>.0) =
hI6 d(I>.0) = -d(I>.o), whence it follows that
d(I>.o) = O.
Similarly, it is easy to see that the IR Al is related to the group GD =
o x R. The singlet and triplet basis functions of the representation Al have
the form
7/!(I>.) = 1(1).), (43.17)
d(/',,) = (e",/\:x + ey"'y + ez/\:z)f(K.). (43.18)
The expressions (43.17) and (43.18) tell us that in the phase G D = 0 x R
corresponding to the IR Al there are no isolated Fermi-surface points or lines
where the conditions (43.15) and (43.16) are satisfied.
Consider the two-dimensional IR E. The basis functions that transform
according to the representation E may be chosen in the form:
{ 7/!1(I>.) = ("'; + f/\:~ + f ",;)/(I>.)

2
S = 0: 7/!2(I>.) = (/\:; + f2/\:~ + f/;;;)/(I>.)
(43.19)
{ dl(~) = (e",K", + f.eyKy + f.2ezKz)f(~)

s= 1: (43.20)
d2(~) = (e",K", + f. 2eyKy + f.ezKz)f(~)
The ordered phases that are described by the two-dimensional representation

E differ in the mixing coefficients of these modes:
S =0 : .,p(~) = '71.,pl(~) + '72.,p2(~)' (43.21)

S = 1: d(~) = eldl(~) + 6d2(~). (43.22)
We now act on the functions (43.21) and (43.22) with the elements of all the
groups CD (43.12) enumerated above and require that the functions .,p( ~) and
d(~) be invariant for each group. From the list (43.12), we thus obtain for
each group CD a system of equations for the coefficients '7i and In most of ei.
the cases the resulting systems of equations have a zero solution: '7i O. = ei =
This means that the corresponding ordered phases CD are not described by
the representation E. The rest of the CD groups allow non-zero solutions:
7J = '7(1,0), e = e(l, 0); CD = O(D2)'

7J = '7(1, I), e= e(1, I); CD = D 4 h(D2 ) x R, (43.23)
7J = '7(1, 1), e= e(1, 1); CD = D 4 (C1 ) x R.
Recall that the analysis performed above applies to the group O. The tran-
sition to the group Oh is realized by adding the color element 925 = {h 25 iOi1r}
= = =
for S 1 and the element 925 {h25iOiO} for S O. Here the two-dimensional
representation E of the group 0 generates two two-dimensional representations,
Eg and E u , even and odd with respect to the inversion. The even represen-
tation Eg describes the transition to the singlet phase S = 0, while the odd
representation Eu describes the transition to the triplet phase S = 1.
The conditions (43.15) and (43.16) for the gap on the Fermi surface to
vanish depend also on the mixing coefficients. We write down the expressions
for the functions .,p(~) and d(~) (these expressions correspond to the mode
mixing types found (43.23)):
CD = D4(D~) x R: {.,p(~) = (K; - K~)f(~) (43.24)

d(~) = (e",K", - eyKy)f(~);
CD = D4(Ct) x R: {.,p(~) = (2K; - K~ - K;)f(~) (43.25)

d(~) = (2e",K", - ezKz - eyKy)f(~).
From the expressions obtained and from the expressions (43.21) and (43.22),
we see that the conditions (43.15) and (43.16) for the phase CD O(D2) are =
398 CHAPTER 10
fulfilled at the intercepts of the Fermi surface with the three-fold axes, that is,
= =
K- ,,(111). For the phase CD D4(D~) x R these conditions are fulfilled for
S = 0 on the lines of intersection of the Fermi surface with the diagonal planes
of the cubic cell, while for S = 1 they are fulfilled at the intercepts of the Fermi
surface with the four-fold axes. Finally, the condition (43.15) for the phase
CD = D 4( Ct) x R is fulfilled in the case of ±"x = ±"y = ±"z = ". In all the
phases except the last, the occurrence of zeros in the gap is symmetry induced
since, just as in the case of a one-dimensional IR, the zeros appear as a result of
the presence of loaded symmetry elements in the group G D. There are no such
elements in the phase G D = D 4 ( Cd x R and the fulfillment of the condition
(43.15) for S = 0 is accidental. Inclusion of concomitant parameters will lead
to the resulting expression for 'I/!(K-) not vanishing at ±"x = ±"y = ±"z = "
[53].
The ordered phases corresponding to the three-dimensional IR's FI and
F2 of the group 0 are found similarly. We write out the chief results [53]. The
functions 'I/!(K-) and d(K-) for the representations FI and F2 have the form:
'l/!2(K-) = "z"x("; - ";)f(K-); d 2 (K-) = (ez"x - ex"z)f(K-); (43.26)

'l/!3(K-) = "y"x("; - ";)f(K-); d 3 (K-) = (ex"y - eY"x)f(K-);
F2 : 'l/!1(K-) = "y"zf(K-); dl(K-) = (ey"z + ez"y)f(K-);

'l/!2(K-) = "z"xf(K-); dAK-) = (ez"x +ex"z)f(K-); (43.27)
'l/!3(t;,) = "y"xf(t;,); d 3 (t;,) = (ex"y + eY"x)f(K-);
The following ordered phases correspond to the non-zero mixing coeffi-
cients of the modes 'l/!i(t;,) and di(K-):
1] = 17(100) FI : G D = D 4 (C4 ) x R, F2 : GD = D 4 (D 2 ) x R,
17 = 1](liO) GD = D 4 (CI ), CD = D 4 (Ct),
(43.28)
1] = 1](111) GD = D 3 (C3 ) x R, GD = D 3 (C3 ) x R
11 = 1](lff2) GD = D 3(Ct), CD = D3(Ct).
The mixing coefficients ~i coincide with the coefficients 1]i and are therefore
not written out in the expressions (43.28). The transition to the group Oh and
its IR's Flu, FIg, F 2g and F 2u is realized in trivial fashion, just as with the
two-dimensional IR E. The information contained in the expressions (43.25)-
(43.28) enables us to find readily the corresponding points and lines of the
Fermi surface where the gap is likely to vanish.
The possibility of the gap going to zero manifests itself in the character
of the temperature dependence of the heat capacity Ce(T). In the case of
the usual superconductivity the exponential dependence Ce(T) .-v exp( -t:J./T)
holds. The vanishing of the gap at isolated points and lines on the Fermi surface
leads to the dependences Ce(T) .-v T2 and Ce(T) .-v T3 respectively [53]. Thus
experimental heat capacity measurements may indicate the type of pairing that
occurs in a given crystal.
THERMODYNAMIC POTENTIALS
We wish to note once again a special feature of the above approach to the
symmetry analysis of ordered phases. Just as was done in §42 in the symmetry
description of commensurate-incommensurate phase transitions whose analysis
calls for color symmetry, the color groups of the low-symmetry phases are
placed in correspondence with the space group IR. It is this factor that is
decisive in the thermodynamic description of such phase transitions in terms
of Landau theory. The thermodynamic potentials for all the IR's considered
above (A 1 , E, F 1 , and F 2 ) have been explored in different sections of this book.
\Ve write them out once again and discuss some of their properties, without
duplicating the complete analysis of these potentials:
<PE = r(1]11*) + U1(1]11*)2 + u2111112117212;

(43.29)
<PF = 1'(1]11*) + U1(1]11*)2 +u2111212 + u3(111114 + 11]21 4 + 11]31 4).
By virtue of the special choice of the basis functions (43.26) of the representa-
tion F1 and of the basis functions (43.27) of the representation F2 , the potential
here is the same in both cases.
The potential 0, U2 > 0);

U1
2. l1]rl = 11]~1 = - 4U1 ~ U2 ; (U1 > 0,U2 < 0).
For the two-dimensional representation E, the 1]4 model contains only the mod-
uli of the complex OP components 1]1 = =
11711e i 1>1 and 1]2 11]2Iei 1>2, so the phases
</;1 and </;2 remain indeterminate. To lift this indeterminacy, we need to allow
for sextic invariants, for example w( 1]~1]23 + 17t31]~). For w > 0 we then have
phase 2 with </;1 - </;2 = 7r /3, while for w < 0 we have the same phase with
</;1 - </;2 = 27r/3.
400 CHAPTER 10
The potential <PF has the following peculiarities. When U2 < 0 the mini-
mum of the potential corresponds to phases with a real vector ",. Phases with
a complex vector '" = ",' + i"," occur for U2 > 0; from the condition for the
potential <PF to be minimal, we find 7]2 = 0, which implies that ",' 1. "," and
117'1 = 1","1· It is convenient to introduce the vector L = [",'","], the direction of
which determines the symmetry of the supe~conducting phase. Thus the vec-
tor L in the phase", = 7](1((2) is directed along a three-fold axis. The phase
'" = 7](liO) corresponds to the vector L parallel to a four-fold axis.
We conclude by noting that the vector L has the physical meaning of
magnetic moment direction, and all the phases described by this vector should
exhibit magnetic properties [53]. Indeed, it is easy to see from the expressions
(43.28) that in phases with a non-zero vector L the symmetry with respect to
time reversal is absent and the element R is involved only in combination with
some base group elements.
In the description of superconducting phase transitions, as can be seen
from the material outlined above, we have repeatedly employed the techniques
expounded in the previous sections of this chapter. In conclusion, we wish to
emphasize some fundamental points of modern phase transition theory that are
of a general character and do not depend on the nature of the phase transition.
In this chapter we have explored in sufficient detail the symmetry aspect of
various phase transitions: magnetic, structural, liquid-phase - quasicrystal, and
superconducting transitions. With these four examples we have investigated
the role of color symmetry in phase transition theory and shown that in addition
to t11e usual classificational meaning, the color groups have a physical content
that is determined by a particular type of thermodynamic potential. Thus the
choice of a color group type in the case of magnetic transitions is associated
with the choice of the most essential interactions and neglect of the others. In
the case of superconducting transitions it is the color loads that determine the
unusual properties of superconducting phases.
Another facet of the color groups has been demonstrated with the example
of incommensurat~ structures and quasicrystals. Owing to the color groups it
has been possible in both cases to achieve agreement between the experimen-
tally observed properties and the symmetry of these structures. Moreover, it is
the color symmetry that has helped to con1prehend the reality of the recently
discovered new type of crystalline state in quasi crystals.
An important feature that unites all the four sections of this chapter is the
relation of the colour groups to the space group IR's. This relation comes from
the isomorphism theorem [58], according to which the color groups treated here
are isomorphic to the space groups. As a consequence, it has been possible to
describe these transitions in terms of the celebrated Landau thermodynamic
theory of second-order phase transitions.
Finally, in the case of superconducting phase transitions we have encoun-
tered for the first time a quantum mechanical order parameter, the role of
which is played by Cooper-pair wave-functions. It is remarkable that in this
case too, one may employ the usual scheme of group-theoretic analysis of phase
transitions, created for classical OP's. The quantum mechanical nature of the
OP has manifested itself in the necessity of introducing color groups. It is
the presence of color symmetry elements that is responsible for the unusual
properties of the superconducting phases.
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CHAPTER 11
Fluctuations and Symmetry
44. Fundamentals of the Fluctuation Phase Transitions Theory
CRITICAL INDICES
The singular behavior of the thermodynamic quantities in the vicinity of the

phase transition is specified by so-called critical indices, which describe the
power-type dependence of these quantities on temperature t = T - Te. The
critical indices are introduced for the susceptibility X, heat capacity C, order
parameter 1], etc. and are determined from the relations
(44.1)
The first two indices have been introduced for temperatures above and below
Te, the index f3 has been determined evidently only for T < Te.
Apart from the indices for the thermodynamic quantities, one introduces
indices that characterize the behavior of order parameter correlations in the
disordered phase and at the phase transition point itself. The correlations are
assumed to decrease exponentially at T > Te and to obey the power law at
T=Te:
(1](0)17(r)} "- e- r/€, (T> Te), (44.2)
1
(1](0)17(r)) "- r d - 2 +1I ' (T = Te) (44.3)
e,
(d is the dimensionality of the space). The quantity that is, the correlation
length, increases indefinitely at T = Te and is characterized by a critical index
v:
(44.4)
The relation (44.3) defines one more correlation length index, namely, the
Fisher index 1].
404
FLUCTUATIONS AND SYMMETRY 405
Of primary concern to the Landau phase transition theory, which was

treated in the foregoing chapters of this book, is the analysis of dissymmetric
phases. In the disordered-phase region (T > Tc) a system that allows only for
OP fluctuations is described in this theory on the basis of a simple Hamiltonian,
(44.5)
taking into account only the fact that there exist fluctuations, that is, that the
OP distribution is non-uniform, and disregarding the interplay of the order pa-
rameters. Statistical averaging with the Hamiltonian Ho leads to the following
expression for the Fourier component of the correlator (7](O)7](r)):
(44.6)
The inverse Fourier transformation leads to the exponential form of the

relation (44.2), where e'" e'"
r- 1 / 2 . Since r'" (T - T c ), this gives r 1 / 2 , that
is, the critical index v = 0.5.
The Landau theory, which employs a zero approximation with respect to
the interaction of OP fluctuations, leads to the following values of the major
critical indices:
'Y = 1, = 0, f3 = 0.5, v = 0.5, 7] = O.

Q' (44.7)
In the sixties, experiment and numerical computations on different models

were found to give a substantial discrepancy of the critical indices from the
values following from the Landau theory. Analysis of a large number of systems
led to the idea of the phase transitions being universal in the sense that the
critical indices do not depend on the intensity of interactions in a system and
on the details of its macroscopic structure, but rather are determined by the
number of OP components and by the dimension of the space.
Prior to the creation in the early seventies of the contemporary phase
transition theory that took into account the strong fluctuation interactions near
T e , supporting the idea of universality and enabling the critical indices to be
calculated approximately and sequentially, a relation was phenomenologically
established that permitted expression of all indices in terms of some two indices.
Two indices are held to be the most fundamental; these are v and 7]. These
similarity relations [1] arise owing to the fact that near Te the correlation length
e increases indefinitely and is the largest of all the length dimension quantities
specifying a system. Such similarity relations can be derived from Patashinskii
406 CHAPTER 11
and Pokrovskii's scaling invariance requirement [1] or from the independent

construction due to Kadanoff [2]. The latter construction proceeds from the
fact that in the vicinity of Tc, where ~ ~ a (with a the lattice spacing) the
initial system of spins on the lattice sites may be replaced by a spin block
lattice and the form of the Hamiltonian should not change as this is done. This
procedure of block enlargement can be repeated until the size of the blocks
coincides with the correlation length, but the latter increases indefinitely as T
approaches Tc.
We quote some of the similarity relations
2(3
d - 2 + TJ = -,
II
dll + 0: = 2, 'Y = (2 - TJ)II, .•• , (44.8)
which state that the critical indices should depend sensibly on space dimension.
It is readily verified that the Landau indices (44.7) for real space d = 3 do not
satisfy these relations, but do so for space d = 4. This immediately points to
the distinct character of space dimension d = 4. Indeed, modern theory [3]
shows that at d = 4 the critical indices of the system are the same as those
of a system with non-interacting fluctuations. This circumstance allows one to
exploit a specific perturbation theory in which the critical behavior of systems
in a four-dimensional fictitious space is used as the zero approximation and then
to make a continuous mathematical transition to a space of lower dimension.
On outlining the fundamentals of the contemporary theory of critical phe-
nomena, we consider in detail the role that the interaction of fluctuations plays
in the description of phase transitions in highly anisotropic systems and discuss
primarily the interaction effects due to their symmetry.
THE RENORMALIZATION-GROUP AND {-EXPANSION METHOD
The peculiarities in the behavior of the thermodynamic quantities in the crit-

ical region arise from the interplay of OP fluctuations and from the indefinite
increase of the correlation length as Tc is approached. The energy of the system
in the symmetric phase near the phase transition has to be described by the
Landau expansion in powers of the OP, in which it is necessary to retain terms
with spatial derivatives that allow for the inhomogeneous distribution of the
OP. This expression for the energy is often called the Ginzburg-Landau Hamil-
tonian H GL . The probability of fluctuations possessing a given configuration
is defined by an expression proportional to exp (-;t;...H
GL ) , so it is convenient
to consider a dimensionless fluctuation energy, !rHGL == H [4].

We write the most general form of the Hamiltonian H in the 1]4 model:
H = J dd x { ~ L: [r1]~ +
).,
('V' 17>Y] + L:
)"PJJII
u).,PJJII 17).,17p1]JJ1]1I } (44.9)
the order parameter here is so normalized that the coefficient of the gradient
term is equal to zero. The expression that we have written includes all the
invariants of degree four for the initial-phase symmetry group and a given IR,
so that U)"PJJII is the sum over all these invariants, that is,
U)"PJJII = L: U~PJJII' (44.10)

P
In the homogeneous case this expression transforms to the usual Landau free-
energy expansion with which we were concerned when investigating the various
dissymmetric phases (the difference lies in the factor of r, which is convention-
ally introduced in writings on fluctuation theory).
In the momentum representation the expression corresponding to the
Hamiltonian (44.9) is
H = ~ Jdq(r+ q2) L:1]).,(q)1]).,(-q)+
J
).,
+ dql ... dq4 U ).,PJJII(ql ... q4)1]).,(qt)1]p(q2)1]JJ(q3)1]II(q4)X

X8(ql+q2+q3+q4), (44.11)
dq = dd q/(27rd) being a volume element of the reciprocal d-dimensional space.

The integration over q is performed up to the cut-off momentum qo < 1/a,
where a is the lattice spacing. This implies that only macroscopic fluctua-
tions are allowed for in H. In this context the momentum dependence in the
quantities uP is normally neglected.
The problem of the phase transition reduces to an analysis of the partition
J
function
z = Sp e-{3HGL = D1]e- H , (44.12)
which is a continual integral over all the values of the OP 1])., (q) between -00
and 00 with a volume element
D1] = II II d1]).,( q). (44.13)

O<q<qo ).,
408 CHAPTER 11
The fundamental idea of the renormalization group approach is to integrate

the expression for the probability exp( -H) over short-wave fluctuations and to
obtain an effective Hamiltonian for long-wave fluctuations. This Hamiltonian
is determined from the relation
(44.14)
in which the integration is carried out with respect to the volume elements
II II d17>. (q) (44.15)
associated with the wave-vector interval qo/b < q < qo (b> 1).
The OP 1]>..(q) for q from this interval is labeled by 1]l>..(q), while for q in
the interval 0 < q < qo/b it is labeled by 1]0>..( q). Thus for any q value in the
complete momentum interval 0 < q < qo the OP may be formally represented
as a sum 1]( q) = 1]0 ( q) + 1]1 (q) of two terms in which either one term or the
other is identically equal to zero.
On integrating with respect to Df/l' the expression (44.14) determines a
Hamiltonian H'[1]o] that involves only long-wave fluctuations 1] and depends on
an arbitrary numerical parameter b. Further transformation of the Hamiltonian
H'[1]o] consists in, first, extending the momentum scale by a factor b, owing to
which the interval of new momenta q' becomes the same as the initial interval,
that is, 0 < q' < qo, and second, varying the scale of the OP 1] by a factor z.
This formal transformation, expressed by the relations
q -+ q' = bq, 1](q) -+ 1]'(q') = z-l1](q) (44.16)
corresponds physically to Kadanoff's idea of a transition from the initial lattice

of 'spins' to enlarged blocks with effective 'spins'.
The transformation from the initial Hamiltonian H to the effective Hamil-
tonian H' by use of the relations (44.14) and (44.16) may be described with
the help of some operator R, the operation of which may be repeated to derive
new Hamiltonians H", Hili, etc.:
H' = RH, H" = RH' = R2H, .... (44.17)
The operators R, R2, R3, ... constitute what is called a renormalization group
[5]. The behavior of a system at the phase transition point is associated with
limiting properties of the renormalized Hamiltonian, namely with the existence

of a fixed point H*, which is defined by the relation
H* = RH*. ( 44.18)
If, under the reiterated operation R, the initial Hamiltonian H tends to a

limiting value H* , the fixed point is said to be stable. The 'rate' of approach to
the stable fixed point determines the critical indices of systems. Thus to probe
a phase transition is to obtain a renormalized Hamiltonian H' (establish the
renormalization-group operation R), find fixed points, and explore the stability
thereof.
There are also other procedural approaches in phase transition theory.
However, in these approaches too, the problem reduces to searching for stable
fixed points of a system of differential equations describing the effective inter-
action of long-wave fluctuations.
The renormalization-group method, developed by Wilson [5], is described
in detail in the monographs by Wilson and Kogut [6], Ma [7], Patashinskii and
Pokrovskii [1,8]. In what follows we briefly outline the essentials of this method
and derive equations requisite for the problem posed, that is, for a discussion
of the role of symmetry in critical phenomena. We will be concerned primarily
with how an effective Hamiltonian H' can be obtained.
We rewrite the fundamental equation (44.14) in the form
(44.19)
where the symbol ( ... )0 denotes averaging over an ensemble of non-interacting

fluctuations, namely
(44.20)
J
Here
HO[1]d = ~ dq(r + q2) L 1]1>. (q)1]lA( -q). (44.21)
>.
We assume that the rescaling (44.16) in equation (44.21) is fulfilled. Therefore
(44.22)
The integration in the last expression is carried out over the interval 0 < q' < qo,
while in H O[1]l] it is over the interval qo/b < q < qo. We dispose of the scale
410 CHAPTER 11
factor in such a way that the term with ql2 in the renormalization expression
(44.22) has the same form as that in the initial equation (44.21), that is,
(44.23)
After such gauging, the Hamiltonian H' will depend only on the parameter b.
The average with respect to the exponent involved in the expression (44.19)
can be calculated using perturbation theory. If we expand the exponent in a
series, the problem boils down to a calculation of the ( ... )0 averages with
respect to the quantities 'T]1. It is easy to show that the theorem that reduces
the product average to pairwise averages (Wick's theorem) is available here:
(44.24)
Each term of the series may be represented graphically according to the fol-
lowing rule: The quantity u)../J.vp is represented by a point (vertex) at which
four lines converge; the free-ended lines refer to quantities 'T]o).. (q), and the lines
that connect vertices refer to quantities (44.24), an integration being carried
out with respect to momenta that correspond to such a line.
Thus the series for (exp( -Hint})O is represented by graphs with different
number of free ends - with two, four, six, etc., part of which are connected
and part of which are unconnected. As usual, the connectedness theorem holds,
according to which the resulting series is reduced to the exponent
(exp{ -Hint ['T]o + 'T]1]})O = exp{ -S['T]o]) , (44.25)
where S['T]o] contains only connected diagrams of the initial series. The relation
(44.19) now yields the expression for the effective Hamiltonian
H'['T]o] = Ho['T]o] + S['T]o], (44.26)
To the lowest order the S['T]o] may be represented in graphic form:
S['T]o] = ) (+ X + }o{ + .... (44.27)
The first of the graphs evidently renormalizes the expression for the free en-
ergy of fluctuations, the second describes the bare interaction of fluctuations,
the third gives the short-wave fluctuation correction for this interaction, the
subsequent graphs (with six ends) describe the triple interaction of long-wave
fluctuations which is induced by short-wave fluctuations, etc. If we confine
ourselves to fourth-order terms, then it is clear that the renormalized Hamil-

tonian has the same form as the bare Hamiltonian. Since the Hamiltonian H'
describes long-wave fluctuations, the momenta may be set equal to zero in all
the terms corresponding to the interaction. Thereupon the Hamiltonian H'
will contain coupling constants u~PI.lV that are independent of the momenta,
just as for the bare Hamiltonian (44.11).
The expression (44.27) for the diagrammatic series is written very schemat-
ically. In it we allow for the topological structure of the graphs in connection
with the fact that each free line should be specified by a definite index A, and
also take into account the number of topologically equivalent diagrams. With
these refinements, the expressions (44.26) and (44.27) give the renormalized
parameters 1" and u ' of the effective Hamiltonian H' in graphic form:
(44.28)
(44.29)
For generality, the quantity l' involved in equation (44.28) is supplied with
the index A for the case if need arises to consider a phase transition that goes
over several IR's. In analytic form these equations are
(44.30)
u~PJ.lV = b'{u>.pJ.lv - 4 L::(u>.pooUOOJ.lv+

00
(44.31)
Here ( = 4- d is the deviation of the dimension from 4, A and B denote graphic

elements with zero momenta at free ends:
(44.32)
B(1' o ,1'o) = c:>

o
I)
= 1
qo/b<q<qo
d q1? .
1'0 + q~ 1'0
1
+ q~
? (44.33)
412 CHAPTER 11
The integration is performed over the range qo/b < q < qo. Such integrals
over the d-dimensional momentum space are calculated with the aid of the
relation
where
(44.34)
is the surface of a d-dimensional sphere of unit radius.
Near T e , where r --+ 0, we may let the arguments in equation (44.33) tend
to zero, whereupon
B(r'7> ro) ~ "'d l qO
qo/.
dqq-f-l =
q-fW - 1)
"'d 0
f
• (44.35)
Renormalization-group equations depend substantially on space dimen-

sion. Wilson has suggested using these in the vicinity of the special value
d = 4, under the formal assumption that the parameter f is small, expanding
in f and then setting f = 1 in the results obtained, which corresponds to the
phase space dimension d = 3. Such an expansion is an asymptotic one. To first
order in the f expansion, it follows from the expressions (44.32) and (44.33)
that
A(r) =
"'4 [h~(1- b2 ) - dnb], (44.36)
B(r, r) = "'4 In b. (44.37)
Before exploring the renormalization-group equations (44.30) and (44.31)

for small f, we write these in some partial but very common form of thermo-
dynamic potentials composed only of squares of OP components. Let
(44.38)
This trinomial for u>'p!-'v assures the required symmetry with respect to all
indices. In this case the fundamental equations (44.30) and (44.31) lead to the
followng equations [9]:
r~ = b2 {r>. + 8u>.>.A(r>.) + 4 L u>'<1A(r<1n, (44.39)

<1
U~p = bf { u>'p - 8u>.>.u>.pB(r>., r>.)-

-8u>.pu pp B(rp, rp) - 16u~pB(r>., rp)-
-4 L uMu<1pB(r<1, n· r<1 (44.40)
<1
These equations are convenient in analyzing phase transitions in particular

systems.
THE ISOTROPIC MODEL
The isotropic (Heisenberg) model is described by the simplest Hamiltonian for

an n-component OP:
(44.41)
This is one of the particular forms of the Hamiltonian (44.11); it corresponds

to a potential of the form
(44.42)
On summing over the index u, the renormalization-group equations (44.39)

and (44.40) reduce to
r' = b2 {r + 4(n + 2)A(r)u}, (44.43)
(44.44)
To start with, we determine the fixed point (r*, u*) on the (r, u) plane of
the parameters of the Hamiltonian. By definition (44.18), this point is found
from the system of equations
r* = b2 {r* + 4(n + 2)A(r*)u*},

( 44.45)
u* = b'{u* - 4(n +8)B(7·*,r*)u*2}.
In addition to the trivial solution r* = u* = 0 (Gauss fixed point), there is also

another solution to the equations. For this solution to be obtained, we need to
substitute into equations (44.45) the expressions (44.36) and (44.37). To first
order in f we then have
(44.46)
This fixed point is called the isotropic or Heisenberg point. The smallness of f
implies also the smallness of the effective fluctuation interaction in the vicinity
of the point, thus justifying the perturbation theory described above, that is,
the possibility of truncating the effective Hamiltonian at the terms'" 7]4.
414 CHAPTER 11
To explore the problem of the stability of the isotropic fixed point, we

linearize the recurrent equations (44.43) and (44.44) in the vicinity of this
point. The linearized equations may be represented as
(44.47)
.6.u' = b>'u .6.u, (44.48)
where .6.r = r - r*, .6.r' = r' - r*, etc. The quantities Ar and Au are deter-
minable from the relations
whence we have, to first order in €,
( 44.49)
The negative value of Au means that when multiple transformations are

applied to the Hamiltonian, the quantity .6.u' tends to zero, that is, the effective
interaction parameter tends to its value u* at the fixed point. The isotropic
point, therefore, is stable. As for the first renormalization-group equation
(44.47), it shows the divergence of the quantity .6.r' under renormalization-
group transformations since b > 1 and Ar > O. According to Wilson's argu-
ments [5], this is because the correlation length diverges at the phase transition
point Te. The quantity Ar defines the critical index 1/ of the correlation length
through the equation [6]
(44.50)
It stands to reason that the index1/ does not depend on the parameter b, which
is chosen arbitrarily.
Using the expression for Ar gives 1/ to first order in f.:
(44.51)
The Fisher critical index 1] is equal to zero in this approximation. Its values
can be found to second order in f.. To this end, the renormalization-group
equations must be supplemented with terms of higher order in the interaction
u. This gives
n+2 2
17= 2(n+8)2€ + .... (44.52)
It is easy to verify that the Gauss point turns out to be unstable for the
Hamiltonian (44.41); thus the critical behavior of the system is, in actual fact,
described by an isotropic fixed point (44.46).
The formulas (44.51) and (44.52) show that the critical indices depend only
on the number of OP components and on space dimension and are altogether
independent of the magnitude of the bare interaction.
Summarizing, recurrent renormalization-group equations may be repre-
sented as differential equations. Consider, in particular, the equation (44.44)
for the interaction parameter. Assume that the quantity b, on which we have
placed only one constraint, namely, b > 1, differs from unity by a small amount
and choose it in the form b = exp t. Allowing for the smallness of f, transform
equation (44.44) up to terms of order'" f2 to
d(u) 2
dt = -fU - 4(n + 8)K4 U , (44.53)
where the derivative du/dt has arisen from the expression (u' - u)/t with t--+
O. The quantity t, which specifies the interval of integration over short-wave
fluctuations in a single renormalization-group transformation, plays the role
of time. It is the condition for solutions to be stationary, du/dt = 0, that
determines the fixed point u* (44.46). Solving a differential equation gives a
path, originating from a starting point that corresponds to the value of u in
the bare Hamiltonian at t = 0 and to a fixed point at t --+ 00 (for an infinite
number of renormalization-group transformations).
45. Critical Behavior of Anisotropic Systems
UNIVERSAL CLASSES
In anisotropic systems, examples of which are crystals, Hamiltonians with mul-

ticomponent OP's contain several fourth-degree invariants and, therefore, are
characterized by several coupling constants uP (p = 1, ... ,P). Under renormal-
ization-group operations they are all renormalized and specified by coupling
constants u'p. The system of recurrent equations following from the general
equations (44.31) or (44.40) may be represented symbolically as
u' = f(u), (45.1)
with u and u' being P-component columns constituted by quantities up. The
fixed point of the transformations is defined by the equation
u* = f(u*) (45.2)
r
416 CHAPTER 11
and the linearized renormalization-group equation (45.1) in the vicinity of the

fixed point may always be written in matrix form:
(u' - u*) = M,,(u - u*), (45.3)
where M" is a Px P matrix that depends only on the number ofOP components
n, space dimension ( and number b.
Renormalization-group transformations 'cause' the point {Ul, U2, •.. , Up },
characterizing the initial Hamiltonian, to 'move' in a path in the parametric
space of the Hamiltonian, the path being described by the renormalization-
group equation (45.1). In the general case the path either terminates at
some stable fixed point (if any) or goes beyond the stability boundaries of
the Ginzburg-Landau Hamiltonian. The latter possibility is discussed in the
section that follows.
The isotropic model, as we have seen, has one stable fixed point u* and all
paths originating at any given u lead to u*. In the general case this is not so. A
system may, in principle, have several stable points, each of which is attainable
within some region of the parameters of the Hamiltonian ('domain'). Another
'domain' may have a stable fixed point of its own. Since the critical behavior
of a system is determined by a stable fixed point, it will be the same for all
systems corresponding to the given 'domain'. All systems that are described by
a Hamiltonian whose parameters lie within one 'domain' are said to belong to
one and the same universal class. This is the generalized concept of universality
for second-order phase transitions. Within a given 'domain' the critical indices
do not, in fact, depend on the magnitude of the Hamiltonian's parameters.
The stability of the fixed point is determined by the eigenvalues of the
matrix .!'vI". These should necessarily be less than unity. It is convenient to
represent the eigenvalues as bAi , then the stability condition consists in the
requirement
=
Ai < 0 (i 1, ... , P). (45.4)
The correlation length index 1/ is determined by renormalizing the parame-
ter r. In the general case, if the transition goes over a reducible representation,
there are several parameters ry (1/ is the IR number). So the corresponding
linearized renormalization-group equation is a matrix equation:
(45.5)
where 1", 1'" and 1"* are columns made up of all components ry and Mr is the
corresponding matrix. We express the eigenvalues of the matrix Mr in terms
of b)..r, setting all Ar > O. The critical index v is determined by the maximal
eigenvalue [10]:
1
v= . (45.6)
maxA r
Vtle conclude the exposition of the general approach by commenting on the
fundamental importance of the concept of the I group in the analysis of critical
phenomena in crystals. As we saw earlier in the text, different phase transi-
tions that go over different IR's (but the same dimension!) may have identical
I groups and be specified by the same Ginzburg-Landau Hamiltonian. Ac-
cording to what has been stated above, all of these transitions should exhibit
similar critical behavior (that is, possess the same critical indices). Along these
lines the body of mathematics concerned with I groups is the mathematical
machinery employed in the theory of universality of phase transitions in crys-
tals.
Later in the text we shall illustrate the universal behavior of phase transi-
tions by several examples, but now we proceed to discuss the role of anisotropy
in simple n-component models.
CUBIC ANISOTROPY
We explore how the critical behavior of an isotropic n-component model changes

when a cubic-symmetry term is added to the Hamiltonian (44.41). For the
Hamiltonian
H = JddxH L [r1]~ +
)..
(\71])..)2] + u1(L 1]~)2 + U2 L 1]1}
)..)..
(45.7)
the renormalization-group equations (44.40) reduce to the following pair of

equations [11]:
u~ = b€{U1 - 4[(n + 8)ui + 6U1u2]K4Inb}

( 45.8)
u~ = b€{ U2 - 4[12u1 U2 + 9u~]K4In b}.
These have four fixed points (ui, U2) for which
l. (0,0), = A2 = f;
A1
1
2. (0, 36 K4)' A1 = 3"f,
f A2 = -f;
3.
(4(n:8)K4'0),
A1 = -f, A2 = -n-4
-f;
n+8
(45.9)
4-n
4. (f f(n - 4))
12K4n' 36nK4 '
>'1 = -f, >'2 =- -f
3n
418 CHAPTER 11
respectively. For each of these points the eigenvalues Ai of the matrix Mu are
indicated. For the points 1 and 2 the stability conditions (45.4) are not fulfilled,
whereas for the other two points the stability depends on the quantity n. For
n < 4 the point 3 is stable, while for n > 4 the point 4 is stable.
For n = 4 the points 3 and 4 turn out to be degenerate, one of the values
of A going to zero. To solve the stability problem, it is necessary in this case to
go beyond the framework of the first order in L Allowance for terms of order
'" (2 shows that when n = 4 it is the point 4 that is stable.
Thus for n ::; 3 the point 3 is stable, while for n ?:: 4 the point 4 is stable.
The point 3 of the Hamiltonian (45.7) coincides with the point of the
isotropic-model Hamiltonian (44.41). For this reason it is often called a Heisen-
berg fixed point. The point 4 is called a cubic fixed point, since it reflects the
cubic symmetry of an (anisotropic) limiting Hamiltonian.
The critical index v is determined, by use of the technique described in
§44, from the recurrent equation for r:
(45.10)
To first order in ( this gives
(45.11)
Using the formula (44.40) now yields the indices v corresponding to the Heisen-
berg (n ::; 3) and cubic (n ?:: 4) fixed points:
(45.12)
n-l
v = ~ + ~(+ ... , n?:: 4. (45.13)
Thus for n ::; 3 the critical behavior of our anisotropic system coincides with
the behavior of an isotropic system. When the cubic anisotropy is included,
the critical behavior in the case n ?:: 4 becomes different.
These results have been generalized in [12], where the isotropic fixed point
is shown to be always stable at n ::; 3 and unstable at n ?:: 4 with respect to
any anisotropic interaction,...., 1]4. Put another way, the critical indices do not
depend on the presence of an anisotropy when n ::; 3 but do for n ?:: 4.
Note that in a cubic-anisotropy system with n ::; 3 the symmetry of the
limiting Hamiltonian at the fixed point, corresponding to the phase transition
point, becomes higher. It coincides with the symmetry of the isotropic-model
Hamiltonian and is described by the rotation group. Such heightening of the

symmetry of a system at the critical point has received the name of an asymp-
totic symmetry [1]. Examples of asymptotic symmetry will be encountered
later in the text.
EXAMPLES OF SYSTEMS WITH MULTICOMPONENT ORDER PARAMETERS
The authors of [13-15] investigate a variety of phase transitions with the num-
ber of OP components n 2:: 4. We quote some of these to illustrate the impact
of various anisotropic interactions on the critical behavior.
To begin with, we consider the structural transition in Nb0 2 with the sym-
metry change p4 2 jmnm ~ [41 ja [16]. The unit cell in this instance increases
in size by a factor of sixteen and the resulting dissymmetric phase is described
by the wave-vector", = (~~~). The latter belongs to a four-arm star {",9}
whose arms are
'" 1 -_ (111)
442' '" 2 -_(111)
442' '"3 -_(111)
442' '" 4 -_(111)
442 .
The dissymetric phase is specified by a one-dimensional IR of the group G".

Thus the phase transition occurs according to a four-dimensional representation
of the parent space group, so that n = 4. For the IR involved, three invariants
of degree four may be set up; the phase transition is then described by the
Hamiltonian
4 4
H= Jddx{~2:[1'1]~+(V1]-,)2] +u1(2:1]1)+
-'=1 -'=1
+U2 ( 1]i 1]~ + 7J5 7J~) + U3 (7Ji 7J5 + 7J17J~ + 7J~ 7J5 + 7J~ 7J~) }. (45.14)
Vve examine another example - the magnetic phase transition in K 2 IrCl 6

(space group Fm3m), which gives rise to an anti-ferromagnetic III-type struc-
ture [17]. This structure is described by the arm "'1 of the six-arm star {",8}:
"'1 = (~Ol), "'2 = (1~O), "'3 = (Ol~),

"'4 = (~Ol), "'5 = (1~O), "'6 = (Ol~).
Magnetic cell doubling occurs along the x axis with which the atomic spins
are aligned, so that the magnetic structure is described by a one-dimensional
representation of the group G". The phase transition, therefore, is specified by
420 CHAPTER 11
a six-dimensional space group representation, that is, n = 6. The corresponding

Ginzburg-Landau Hamiltonian has the form
H= J dd X { ~L
A=l
6
[1'17~ + (vr l7>Y]

6
+ U1 L 171+
A=l
+u2(l7Il7l + 17~17~+ 17517n+
+u3(l7il7~ + l7il7~ + l7~l7l + l7ll7~ + l7I175 + l7ll7~+
+l7Il7~ + l7l175 + 17~175 + 17~17~ + 17~17~ + 17~175}. (45.15)
By transcribing the OP components, both Hamiltonians (45.14) and (45.15)

may be represented in unified form. Thus for 17 = 4 we write {171, 1727h, ih}
instead of {171, 172, 173, 174}, etc. The expressions (45.14) and (45.15) then result
from the generalized Hamiltonian for a 2m-component OP:
H= J ~ f.=1
dd x { [1'(17; + 77;) + (vr l7.)2 + (vr 77.)2}+
m m
+U1 L(l7; + 77;) + U2 L 17;77;+

.=1 .=1
m
+U3 '" ( 2 2
~ 17.17.' + 17.17.'
2 -2 + -2 2 + -2 -2 }
17.17.' 17.17." (45.16)
.<.'
with m = 2 and 3 respectively.
The renormalization-group equations for the Hamiltonian (45.16) have the
form [14]
1" = b2{r + [12u1 + 2U2 + 4(m - 1)u3]A(1')}, (45.17)

u~ = b {U1 - [36ur + u~ + 2( m
f - 1)u5] 11:4 In b},
u; = bf {U2 - [24u1U2+8u~+4(m-1)u5]1I:41nb}, (45.18)
u~ = b {U3 - [24u 1U3 + 4U1 U2 + 4mu5] 11:4 In b}.

f
The last three equations determine eight real points in (U1 U2U3) space (Table
11.1). Analysis shows [14] that only the points 5 and 6, as functionals of the
quantity m, may be stable. At the point 5 (u; = Us = 2ui) the limiting value
of the Hamiltonian is isotropic:
(45.19)
so this point should be called an isotropic one. This isotropic point is stable
when the number of OP components is less than four, 2m < 4. Otherwise, that
is, when 2m > 4, it is the point 6 that is stable. Inspection of Table 11.1 shows
that with m = 2 (that is, n = 4) the points 5 and 6 coalesce to first order in f.
The stability of this point is verified by making allowance for the ""' (2 terms.
Indeed, the point turns out to be stable.
Table 11.1
Fixed points of the renormalization-group transformations for
the Hamiltonian (46.16)
N ui u:; Us
1 0 0 0
2 1/40 2ui 0
3 1/36 0 0
4 1/72 1/12 0
5 1/8(m + 4) 2ui 2ui

6 (m - 1)/8{5m- 4) 2ui 2ui/(m - 1)
7 1/72(2 - l/m) 1/12m 1/12m

8 1/72(1 + l/m) 1/12{1- l/m) 1/12m
The u; are expressed in terms of K u /(
Using equation (45.17), we find the expression for the critical index v:
v=; r
= !+![6ui+u;+2(m-1)u;]K4' (45.20)
For 2m > 4 the critical behavior is determined by the point 6 and the relation
(45.20) yields
1 3 m-1
v = 2" + 4: 5m _ 4 ( + .... (45.21)
We cite also the expression for the critical index 'f/ [14]:
(45.22)
422 CHAPTER 11
At m = 2 (that is, n = 4) the critical behavior is determined by the

isotropic fixed point 5 and the expression (45.20) gives
1 1
v = 2 + g{+ .... ( 45.23)
This expression coincides with the value of v in an isotropic model with n = 4

(see equation (44.51)); the same applies to TJ.
Thus, as in the cubic anisotropy case treated in the previous section, with
the number of OP components being low, the critical-point behavior of the
system is isotropic; at large n the system shows anisotropic behavior. In con-
tradistinction to cubic anisotropy, the system in the present case with n = 4
remains isotropic. This is another example of the existence of an asymptotic
symmetry.
As noted in the beginning of this section, the Hamiltonian (45.16) describes
at n = 2m = 4 a structural phase transition in Nb0 2 over a four-arm star. The
papers [13-15] report a large variety of magnetic phase transitions that are
described by the same Hamiltonian with the same value n = 4. Here belongs
the transition to an SS-type helical magnetic structure which is observed in Ho,
Dy, and Tb. In the hexagonal crystal p6 3 / mmc the magnetic ordering goes
over the two-arm star of the wave-vector (0,0, K). The atomic spins lie in the
basal planes and are described by a two-dimensional IR of the group G". The
associated space group representation thus is four-dimensional.
TbAu2 and DyC 2 display a magnetic ordering to a modulated TSW (trans-
verse spin wave) structure with wave-vector (K, 0, 0) and spins lying along the
principal axis of the tetragonal crystal (space group J4/ mmm). The wave-
vector star is composed of four arms, and the group G" IR is one-dimensional.
The phase transition is described by the Hamiltonian (45.16) with a special
relation for the parameters: U2 = 2Ul. As can be seen from Table 11.1, the
stable fixed points 5 and 6 of the general Hamiltonian (45.16) are also the fixed
points of this special Hamiltonian. Despite a substantial difference in initial-
phase symmetry, the utter dissimilarity of the structures that arise, and also
the difference in the physical nature of the phase transitions described, all the
aforementioned systems should exhibit similar critical behavior. Specifically,
the critical index v is given by the expression (45.23). To within terms of order
'" (2 we have in this case v = 0.70. The same is true of 2m = 6. As already
stated, the Hamiltonian (45.16) in this case describes the magnetic ordering in
K 2 IrCI 6 . According to [13], the same Hamiltonian (with U2 = 2ud describes
the magnetic transitions in TbD 2 (space group Fm3m) and Nd (space group
p63/mme). In either case we deal with a modulated structure such as a lon-

gitudinal spin wave (LSW) with a wave-vector (/i:00) that generates a six-arm
star. The atomic spins are parallel to the wave-vector and are described by
a one-dimensional representation of the group G". Thus six-component pa-
rameters occur here. For the systems enumerated above, the formula (45.21)
gIves
1 3
v = 2" + 22f + ....
To within'" f2 this yields v = 0.69. For the isotropic model with n = 6, as
follows from the formula (44.51), v = 0.73.
The analysis performed above is a splendid illustration of how the univer-
sality in the critical behavior of systems arises in the renormalization-group
and f-expansion method. The authors of [15-18] give other examples of the
realization of physical systems with number of components greater than four,
namely with n = 8 and 12, for which renormalization-group analysis shows
the existence of a stable fixed point and, consequently, predicts a second-order
phase transition.
46. Fluctuation-Induced Break-Down

to First-Order Phase Transitions
THE ABSENCE OF STABLE FIXED POINTS
Thus far we have encountered examples in which the renormalization-group

equations lead to at least one stable fixed point responsible for the behavior of
a system near a second-order phase transition. With increase in the number of
OP components and in the number of parameters of the Hamiltonian describ-
ing the interaction of the Hamiltonian, a situation is likely to occur in which
none of the fixed points will be stable. The renormalization-group equations
then move, in the Hamiltonian's parametric space, the point corresponding
to the bare Hamiltonian in paths that go beyond the stability boundaries of
the Hamiltonian. It is such examples that were encountered by the authors of
[19,20,21] who concluded that the system would in these cases make a first-order
transition. This new phenomenon - the change from second-order (according
to the Landau theory's criteria) to first-order phase transition due to fluctua-
tion interaction - is, as found by the same authors, rather typical of systems
with a large number of OP components.
As an example, we consider the magnetic phase transitions in the cubic
crystals TbS, TbP, and TbSb, which have the space group Fm3m. The result-
424 CHAPTER 11
ing magnetic structure belongs to type II ferromagnets in the f.c.c. lattice. In

this lattice the ferromagnetic (111) layers with the spin direction [111] alter-
nate, producing an anti-ferromagnetic order. The wave-vector of this structure
( ~ ~ ~) generates the four-arm star
K _(111) K _(111) .,. _(111) ... _(111) ( 46.1)

1 - 222' 2 - 222' '''3 - 222 ' '''4 - 222'
Since the atomic spins are parallel to the wave-vector, the structure is described
by a one-dimensional representation of the group G,., therefore the phase tran-
sition is specified by a four-component OP and the Hamiltonian [15]
H = J
dd x {
4
~ 2: [r1]~ + (V'1]>Y] + U1 (2: 1]n 2+
A=l
4
A=l
4
+U2 2: 1]1 + U31]11]21J31]4}' (46.2)
A=l
The recurrence equations
U~ = bf {U1 - [48ui + 24u1U2 + ~U~] }/\:4Inb,

U~ = bf {U2 - [36ui + 48u1U2 - ~U~] }/\:4In b, (46.3)
U~ = bf {U3 - 48u1U3J{4Inb}
have four fixed points
1 (0,0,0), 2 (0 _t_ 0) " 3 4 (_t_

, 36"4 '
...:.:... ±t)
48/\:4 72/\:4 6"4
with positive Ai, which are therefore unstable. Besides, there is also the
isotropic fixed point 5( 48~4 ' 0, 0), for which two values of A are equal to zero to
first order in t. To solve the problem of its stability, it is necessary to elevate
the accuracy of equations (46.3) by including terms of order,..., t 2 into these
equations. In this approximation the point 5 turns out to split up into four
fixed points, all of which are unstable.
FIRST-ORDER PHASE TRANSITIONS IN MAGNETIC SYSTEMS
A similar situation is observed in the examples enumerated in Table 11.2. The

table gives the space group G for the paramagnetic phase of a crystal, the type
of magnetic structure (alongside the wave-vector and spin orientation relative to
it), the number of star l{,,} arms and the number of OP components. In keeping
Table 11.2
Magnetic systems for which the renormalization-group equations have no
stable fixed points [21]
Material G Magnetic structure I{,,} n
U0 2 Fm3m Acl) - I, '" = (100), s .1 '" 3 6
TbAs,TbSb,TbP Fm3m Acl) - II, ",-ell)

- 222' sll'" 4 4
CeS,TbSe,NdSe
NdTe
MnO,NiO,MnSe Fm3m Acl) - II, ",-ell)

- 222' s.l", 4 8
a-MnS,ErP,
ErSb,EuTe
Cr Im3m TSW, '" = (11:00), .1 '"

S 6 12
Eu Im3m SS, '" = (11:00), ..1 '"
S 6 12
,a-Mn [36] F43m Acl), '" = (~10), s II '" 6 6
MdSn3 [37] Pm3m Acl), '" = (~OO), s .1 '" 3 6
with the Landau theory's criteria, the phase transition in these materials should
be of second order; however, none of these systems has stable fixed points [21]
and it is therefore assumed that the phase transition in the systems involved
should be a first-order transition. In respect of U0 2 , MnO, Cr and Eu it
is known that the magnetic phase transition in each of them is a first-order
transition.
A detailed analysis of the instability of fixed points for the magnetic phase
transitions listed in Table 11.2 has been given and possible types of first-order
phase transitions determined in [19,20].
We have considered examples of a fluctuation-induced break-down of phase
transitions to first order in systems that have no stable fixed points. However,
in anisotropic systems one may encounter situations in which a system does
have a stable fixed point but the region of its attainability is confined in the
426 CHAPTER 11
parameter space of the Hamiltonian. For some initial values of the Hamiltonian,
which lie outside the accessible region, the phase transition breaks down to a
first-order transition [22-24].
It should be noted that the conclusion that in a system where a stable fixed
point is absent, the phase transition should be of first order has been drawn
from an analysis of the renormalization-group equations in (4 - f)-space. In
three-dimensional space the behavior of such a system may turn out to be more
complicated. Thus no stable fixed point has been found in anti-ferromagnetic
N dSn3. At the same time experiment has not shown that a first-order phase
transition takes place: The OP decreases with temperature continuously and
there is no hysteresis, but the critical scattering indispensable for the phase
transition to be viewed as a second-order transition has not been detected
either. The physical nature of the magnetic phase transition observed remains
to be ascertained.
As a concrete analysis [19-21] shows, the absence of stable fixed points
is a phenomenon typical of systems with a large number v of independent
invariants of degree four (and, consequently, with a large number n). However,
as shown in reference [25] of Chapter 1, there are examples of systems with
a large number of invariants v > 3 in which a stable fixed point exists and,
therefore, there (1re no topological constraints on its existence in the general
case. It might be well to point out also that the author of the above-cited paper
has obtained a very strong result: With the number of OP components n being
greater than 4, there is only one stable fixed point (if it exists). It corresponds
to a second-order phase transition, the symmetry of the Hamiltonian at this
point being higher then the symmetry of the system itself and being described
by the group SO(n).
47. Fluctuations in the Vicinity of Multicritical Poiuts
SYSTEMS WITH COUPLED ORDER PARAMETERS. BICRITICAL AND

TETRA CRITICAL POINTS
e
In §20 we considered the problem of two interacting OP's 1] and within the
framework of the mean-field approximation. The coefficients rl and r2 of the
terms 1]2 and e in the thermodynamic potential depend on temperature T and
some parameters X, for example pressure, concentration, etc. Two second-
order phase transition lines, determined by the equations
rl (T, X) = 0, r2(T, X) = 0, (47.1)

may intersect at some point (Te, Xc), in the vicinity of which the interaction
between the subsystems described by the quantities TJ and is substantial. e
As we saw, as a function of the magnitude of the interaction between the
subsystems, two different phase diagram types arise. These are diagrams with
a bicritical point and diagrams with a tetracritical point, which does not allow
e
the existence of phases with TJ f:. 0 and f:. 0 (Fig. 11.1). The fluctuations
may largely affect the behavior of the phase transition in the vicinity of the
intercept (Te, X e) and give rise to other phase diagram types.
T T
\ //
\ /
/
/
\/
A
,,
x
a) 0)
Fig. 11.1. Phase diagrams with bicritical (a) and tetracritical (b)
points in Landau theory.
'-IVe explore the critical phenomena in a system of coupled OP's by the

example of a Hamiltonian of a very general form:
H = Jddx{~ [rlTJ 2 + l'2e + (\i'TJ)2 + (\i'e)2] +
+Ul17 4 + U2e 4 + 2U3TJ2 e} (47.2)
Let TJ = {TJ1, ... , TJn} be an n-component parameter and = em} an 171-e {el, ... ,
component parameter and let them belong to two different IR's of dimensions
nand 171. There is no anisotropy in this Hamiltonian, a fact which enables
one to trace the dependence of the critical behavior solely on the numbers n
and 171. A complete analysis of the problem of the phase transition in such a
system has been performed in [26] and (independently, by invoking Wilson's
renormalization-group technique) [27]. Taking into account the fundamental
importance of this example, we reproduce here the major steps of the analysis.
Vve assume the quantities rl and r2 to go to zero in the general case at
different temperatures (which, independently, may coincide in particular cases),
so that the OP's may fluctuate in different ways and should be independently
renormalized with the help of the associated quantities Zl and Z2 (see the second
428 CHAPTER 11
of the relations (44.16)):
The general renormalization-group equations (44.39) and (44.40) for the

Hamiltonian (47.2) reduce to the following system:
r~ b
= Zrb-d + 4(n + 2)A(rt}u1 + 4mA(r2)u3] '
(47.3)
1'; = Zib- d [1'2 + 4(m + 2)A( 1'2)U2 + 4nA(rdu3] ,
u~ = Ztb-3d(ul-4[(n+8)ui+mu~]"41nb),
u~ = Zib- 3d (u 2 - 4 [(m + 8)u~ + nU5] 1>:4 In b), (47.4)
u~ = Z? Zib- 3d (u3 - 4 [(n + 2)U1 U3 + (m + 2)U2U3 + 4u5] "4 In b).

Suppose we are far from the point of intersection of the phase transition
lines r1 = 0 and r2 = 0, but near 1'1 = O. Under these conditions the OP
T) fluctuates strongly, whereas the fluctuations of e are small. For a strongly
fluctuating parameter we should choose the general normalization (44.23), that
is, set Zl = p+d/2. To a zero approximation with respect to the interaction, the
first of the equations (47.3) leads to the relation ri = b2r1. At the same time
the r2 should remain unrenormalized (r~ = r), which is achieved by choosing
Z2 = bd/ 2. With this choice of Zl and Z2 the recurrence relations have the
structure
U1I '" b4-d , u2I '" b-d ,u3I '" b2-d . (47.5)
At d = 4 - ( the last two relations lead, after repeated iterations of the

renormalization-group operation, to zero values of u~ and u~; thus only one
of the three equations (47.4) persists in the limit:
(47.6)
The first of the equations (47.3) in this case reduces to
(47.7)
Thus, on eliminating immaterial interactions in the system under con-

sideration, the full renormalization-group equations for two interacting OP's
have reduced to the familiar equations (44.43) and (44.44) of the n-component
isotropic model. The critical behavior of the system is determined only by the
Table 11.3
Fixed points for the system oftwo coupled order parameters, described
by the Hamiltonian (47.2)
N u*1 u*2 u*3 >'i (x, y)
0 0 0 0 { { { -
1
1 n+8 0 0 -{ {
(n!8){ (1,0)
2 0 n+8
1
0 { -{
(m~8){ (-1,0)
32-2(n+m)-nm
3 1
n+8 n+8
1
0 -{ -{
(n+8)(m+8) { (n;~;16'0 )
1
4 n+m+8 1 1 8 n+m-4
n+m+8 n+m+8
-{
-n+m+8{ n+m+8{ (0, ~)
5 u*1 u*2 u*3 >'1 >'2 >'3 (x, y)
Up in terms of ~.
strong fluctuations of one ofthe components, so that the critical indices depend
only on the number of components n of the strongly fluctuating parameter.
At the intercept r1 = r2 both parameters fluctuate strongly, so it is nec-
essary in equations (47.3) and (47.4) to choose Zl = Z2 = b1+ d / 2 , whereupon
the right-hand side of each of the equations will contain the standard factor bf •
To first order in { the equations (47.4) have six fixed points (Table 11.3).
Examination of Table 11.3 shows that the first three points are unstable.
The stability of the points 3 and 4 is determined by the respective inequalities
2(n + m) + nm > 32 (for point 3); n + m < 4 (for point 4) . (47.8)
For the point 5 all the three values of ui are non-zero [27]. The stability
regions of the points 3, 4, and 5 on the (n, m) plane are shown in Fig. 11.2.
The point 3, for which the interaction parameter of two subsystems is equal
to zero, refers to the critical behavior of uncoupled systems. The point 4 is
isotropic, because the limiting Hamiltonian
(47.9)
at this point corresponds to an isotropic model with the number of components

n + m. Thus we have met with one more example of asymptotic symmetry [1].
430 CHAPTER 11
Fig. 11.2. Stability regions of fixed points 3, 4, and 5 for the Hamil-
tonian (47.2) [27]. a, line n +m = 4; b, line 2(n + m) + nm =32.
The equations (47.3) for this fixed point degenerate to one equation (44.43) of
the isotropic model with the number of components n + m. The correlation
length indices may be calculated from the formulas (44.52) and (44.53) with
n replaced by n + m. According to the relation (47.8), the isotropic point is
stable only when n + m < 4; in the case of n + m = 4 one of the Ai values
for it is equal to zero, and to solve the stability problem an analysis to second
order in (02 is required. The authors of [26] maintain that the isotropic point is
unstable for n + m = 4.
Now we have to determine the regions in the parametric space ofthe Hamil-
tonian that correspond to each stable fixed point. The positive-definiteness
region for the quartic form of the Hamiltonian (47.1) is determined by the
inequalities [26]
(47.10)
The phase diagrams for the Hamiltonian (47.1) in the mean-field approximation
(when fluctuations are disregarded) were explored in §20, where we found that
for
(47.11)
a tetracritical point occurs in a system with two coupled OP's and, conse-
e
quently, a mixed phase with 7J :I 0 and :I 0 may exist. Otherwise, when
(47.12)
the phase diagram has a bicritical point, and no mixed phase arises.
Let us ascertain which of the relations, (47.11) or (47.12), the parameters
of the Hamiltonian satisfy at the fixed points. It is convenient to introduce the
FLUCTUATIONS AND SYivIMETRY 431
!J
-f
Fig. 11.3. Phase diagram for a system of two coupling order pa-
rameters at n = m = 1. 1-5, fixed points of renormalization-group
transformations.
variables
x = (Ul - U2)(Ul + U2)-1, y = U3(Ul + U2)-1, (47.13)
in terms of which the conditions (47.10) become
(47.14)
On the (x, y) plane these inequalities cut out the stability region of the Hamilto-
nian (47.2) (Fig. 11.3). Within the ellipse the tetracriticality condition (47.11)
is fulfilled, while outside the ellipse the bicriticality condition (47.12) is satis-
fied. Thus in the mean-field approximation the system should exhibit at the
intercept of the phase transition lines (rl = r2) a first-order transition outside
the ellipse and a second-order transition inside it.
Let us see what changes these regions undergo when fluctuations are taken
into account. To this end, we need to draw the phase portraits that follow
from the recurrence relations (47.4). Given on the (x, y) plane is a schematic
portrayal of the renormalization-group transformation paths for the specific
case n = m = 1.
A stable fixed point here is the point 4. The region of its accessibility
lies between the separatrices 1-5,5-2, on the one hand, and 1-3, 3-2, on the
other. If the bare constants of the Hamiltonian (47.1) lie outside this region,
the phase pathways go beyond the stability boundaries of the Hamiltonian. In
432 CHAPTER 11
this case the phase transition from a disordered to a condensed phase (11 =F 0
e
or =F 0) will be of first order.
If the bare constants lie within the delineated region, then the situation
becomes complicated: The character of the phase transition depends also on
the locus of the point for the bare Hamiltonian in this region. If the point
lies between the separatrices 1-3, 3-2 and the curve 1-4-2, then the phase
transition will be of second order and have a tetracritical point on the phase
diagram [26]. Beyond this part of the accessibility region of the point 4, in
the vicinity of the intersection of the phase transition lines rl = 0 and r2 = 0,
segments arise on these lines that correspond to first-order phase transitions
[26]. Evidently, the size of these segments is determined by the size of the
critical region, in which the interaction of fluctuations is essential. Outside the
critical region the phase diagram structure is given by predictions of mean-field
theory. Recall that within region bounded by the ellipse there is a tetracritical
point and outside the ellipse a bicritical point.
~, t "-
.... - x
Fig. 11.4. Phase diagram with a tricritical point.
Summarizing, we note that the results presented above apply to the case
n = m = 1 only. In the general case the phase plane will be non-symmetric
and the stable fixed point will not necessarily be isotropic. Each particular
case calls for an individual phase diagram analysis.
The critical behavior of phase transitions in a number of crystals, described
by the Hamiltonian (47.2) allowing for the crystalline anisotropy, was studied
in a similar way in [28].
We now proceed to explore the role of fluctuations in other singular phase
diagram points.
The tricritical point is defined as a point on a phase transition line where
the second-order phase transitions are succeeded by first-order transitions
(Fig. 11.4). At the bicritical and tetracritical points there converge two and
four second-order phase transition lines respectively. At the tricritical point
three such lines converge [29,30]. This can be seen only in a phase diagram
in the space of three variables, where it is necessary to consider, along with
T and the thermodynamic force X, one more thermodynamic force, Y. An
example of a system with a two-component OP that allows the existence of a
tetracritical point was described in §25. Inspection of Fig. 7.8, which gives the
phase diagram, shows that, indeed, three second-order phase transition lines
converge at the tricritical point.
The simplest system, in which the situation depicted in Fig. 11.4 manifests
itself, is described by the potential (§25)
(47.15)
At u > 0 this potential describes a second-order phase transition, and for

u < 0 a first-order transition, so that the tricritical point is determined by two
equations:
(47.16)
An analysis of the fluctuations at the critical point may be performed

using the renormalization-group method [31]. Clearly, since the coefficient of
the fourth degree in TJ is equal to zero at this point, one needs to take into
account the term of degree six with respect to TJ and to write the. recurrent
equation for the coefficient v. To second order in the term vrl the recurrent
equation for v will evidently involve the quantity
(47.17)
where the integration is carried out in the momentum interval qo/b < ql, q2 <
qo. To estimate this integral, it is necessary to pass over to the spherical system
of coordinates for the vectors ql and q2 and then, on integrating over the
moduli of ql and q2, to introduce the polar system (ql = qcosB, q2 = qsinB).
In the 2d-dimensional integral (47.17) the integration over the variable q will
then be separated out, so that
(47.18)
where the integration is carried out over the interval b-1qo < q < qo. From this
it is seen that for d = 3 a logarithmic divergence occurs in the long-wave limit
(the integral is proportional to In b), and at d> 3 the integral converges. Thus
for the tricritical point the quantity d = 3 is a critical dimension above which
434 CHAPTER 11
the energy corrections due to fluctuation interaction are finite, and the critical
behavior at this point is described by classical estimates of Landau theory.
The dimension of real space emerges on the upper critical dimension d =
3. In this boundary case the critical indices cannot alter due to fluctuation
interaction, but there arise multiplicative logarithmic additions to all power-
type temperature dependences [31].
LIFSCHITZ POINT
Consider now the critical behavior of a system that has a Lifschitz point on
the phase diagram. This point lies on the disorder-order phase transition line
and is characterized by replacement of the homogeneous phase by a modulated
phase with a zero modulation wave-vector (Fig. 9.2). The Hamiltonian of the
system tolerating the existence of such a point may be chosen in the form [32]
( 47.19)
with rJ = {rJl,' .. ,rJn} being an n-component OP. It is assumed here that the
entire d-dimensional space may be divided into two sectors: One of them,
of dimension m and indexed by I, contains a modulation wave-vector; in the
other, of dimension d - m and specified by the index c, there are no modulation
wave-vectors.
The Hamiltonian (47.19) is a gener alization of Michelson's thermodynamic
potential (35.1), written for a one-component OP and d = 1. (As is customary
in the fluctuation theory of phase transitions, a coefficient 0.5 is placed before
the quadratic terms in the Hamiltonian.)
At the Lifschitz point
(47.20)
so one should allow for the term with the square of the second derivative with
respect to the coordinates of sector I and take f3 > O.
In the momentum space the expression for the Hamiltonian (47.19) is
H = ~ J dd v ( q)rJ( q)rJ( -q)+
J
u dd ql ... dd q4c5(ql + .. . q4)(rJ(qdrJ(Q2)) (1J(q3)1J(Q4)) , (47.21)
where
(47.22)
Here q1 and qc are the moduli of the vector q, if it belongs to the sector I and
c respectively, so that
d
q; = E q;. (47.23)
Q=m+l
Exploiting the techniques described in §44, we write the renormalization-

group equation for the Hamiltonian (47.21) in the vicinity of the Lifschitz point
(-, = 0). In doing this, we need to allow for the fact that the scaling parameters,
which change the scale with respect to momenta (see the first of the relations
(44.16)), should be independent for the momenta contained in the sectors c
and I; we call these b and a respectively. Instead of the recurrence equations
(44.43) and (44.44) for the n-component vector model, we now have [32-34]
We dispose of the parameters a and b in such a way that the terms with
q~ and qJ remain invariant. This leads to the equations
(47.26)
from which we find

(47.27)
The equations (47.24) and (47.25) lead to equations that give the renor-
malization of rand u:
r' = b2 {r + 4(n + 2)uA(r)}, (47.28)
u' = b'{ u - 4(n + 8)u 2 B(r, r)}. (47.29)
Here we have introduced the notation for the integrals
(44.30)
in which the integration is carried out over the momenta: qo/b < qc < qo and
qo/a < g1 < qo; also we have denoted
m
(= 4+ - - d. (47.31)
2
436 CHAPTER 11
For <0, successive application of the recurrence equation (47.29) results in

°at the fixed point. Thus for the space dimension d> 4 +
f
u* = m/2 the fixed

point is Gaussian, and the critical behavior of the system will be classical, that
is, it will coincide with the predictions of mean-field theory. The critical space
dimension for the system at the Lifschitz point is 4 + m/2 instead of 4 in the
usual situation. For d less than the critical value we have f > and the fixed °
point of equations (47.28) and (47.29) may be separated out to first order in
the parameter f, which we will assume to be small.
The integrals (47.30) can be evaluated for small values of r, that is, near
the critical point. For small f we have
A(r) = A(O) - rB(O, 0), (47.32)
B(O, 0) ~ Kdm l qO
qo/b
q-f- 1dq ~ Kdm In b, (47.33)
where Kdm ~ KmKd_m/2(2Km/2)-1. The quantities Kn are given by the

formula (44.34). It is easy to see that when m = the quantity Kdm is equal°
to K4 and we arrive at the familiar theoretical result (44.37) in 4 - f space.
The recurrence equations (47.28) and (47.29) define a stable fixed point
r
*
= -f n
n+2
+8 q5
2' *
u = f
[4}' (n + 8)]-1 ,
idm (47.34)
which coincides in form with the Heisenberg fixed point (44.46) for d = 4 - f.
In the vicinity of the fixed point, the equation (47.28) may be represented in
the standard form
(47.35)
or, allowing for the relation b = a 2 , as
(47.36)
2(
Ar = b 1 - f
n+2 )
n + 8 In b . (47.37)
The equations (47.35) and (47.36) yield expressions for the critical indices
ec and eI
of the correlation length:
1 1 In+2
Vc = Ar = 2 + 4' n + 8 f + ... , (47.38)
1 1 In+2
VI = 2Ar = 4' + 8n + 8 f + .... (47.39)
The quantities ec specify the correlations of fluctuations in the d-dimen-

sional space sector c, and the eI those in the sector I. Thus the critical indices
v for correlations in the directions where a modulated phase arises and those
for correlations in other directions differ by a factor of two.
The presence of two correlation lengths is a distinctive feature of the criti-
cal behavior at the Lifschitz point. The usual correlation length is specified by
the critical index V c , which coincides in form with v for the n-component vector
model (cf. formulas (47.38) and (44.51)). The difference between these expres-
sions lies in the parameter f being determined in different ways. Even in the
case of modulation in one direction (m = 1) the critical dimension u + m/2 for
the Lifschitz point is equal to 4.5. Unfortunately, for the real space the para-
meter f = 1.5 is large; nevertheless, in order to verify the theory expounded,
it is of great interest to investigate experimentally the critical behavior at the
Lifschitz point. Experimental data on multicritical points are contained in the
review [35].
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Appendix
List of cubic-group symmetry elements
hI-I, h2-2x, h3-2y, h4-2z, h5-3 111 , h6-3 111 , h7-3 111 , hS-3 111 ,
l
h9-3 1 1, hlO-3~ll' hll-3~/I' hI2-3 I /1 , hI3-2xy , hI4-4z, hI5-4;1,
hI6-2 xy , hI7-2gx, hlS-2 yz , hI9-4x, h20-4;1, h21-2xz, h22-4- 1
Y ,
h23-2 xz , h24-4y.
List of hexagonal-group symmetry elements
HI-I, H2-6 z , H3-3 z , H4-2z, H5-3;1, H6-6;1, H7-2 y, HS-2 xy ,

H9-2x, HI0-2 210 , Hll-2 xy , HI2-2 120 .
Rotations matrices R~f3 of vector r(xyz) for cubic-group elements
hI h2 h3 h4
1 0 0 1 0 0 -1 0 0 -1 0 0
0 1 0 0 -1 0 0 1 0 0 -1 0
0 0 1 0 0 -1 0 0 -1 0 0 1
h5 h6 h7 hS
0 1 0 0 1 0 0 -1 0 0 -1 0
0 0 1 0 0 -1 0 0 1 0 0 -1
1 0 0 -1 0 0 -1 0 0 1 0 0
h9 hl0 hll h12
0 0 1 0 0 1 0 0 -1 0 0 -1
1 0 0 -1 0 0 1 0 0 -1 0 0
0 1 0 0 -1 0 0 -1 0 0 1 0
439
440 APPENDIX
h13 h14 h15 h16

0 -1 0 0 -1 0 0 1 0 0 1 0
-1 0 0 1 0 0 -1 0 0 1 0 0
0 0 -1 0 0 1 0 0 1 0 0 -1
h17 h18 h19 h20
-1 0 0 -1 0 0 1 0 0 1 0 0
0 0 -1 0 0 1 0 0 -1 0 0 1
0 -1 0 0 1 0 0 1 0 0 -1 0
h21 h22 h23 h24
0 0 -1 0 0 -1 0 0 1 0 0 1
0 -1 0 0 1 0 0 -1 0 0 1 0
-1 0 0 1 0 0 1 0 0 -1 0 0
Rotation matrices R~{3 of vector 1'( xyz)

for hexagonal group elements
HI H2 H3 H4
1 0 0 1 -1 0 0 -1 0 -1 0 0
0 1 0 1 0 0 1 -1 0 0 -1 0
0 0 1 0 0 1 0 0 1 0 0 1
H5 H6 H7 H8
-1 1 0 0 1 0 -1 0 0 0 -1 0
-1 0 0 -1 1 0 -1 1 0 -1 0 0
0 0 1 0 0 1 0 0 -1 0 0 -1
H9 HI0 Hll H12
1 -1 0 1 0 0 0 1 0 -1 0 0
0 -1 0 1 -1 0 1 0 0 0 1 0
0 0 -1 0 0 -1 0 0 -1 0 0 -1
Index
AS6Mn14 373, 380, 383, 387 Ferroics 202

Amplitude FeSn2 360, 362
harmonics 305, 309, 332 Fixed point 409, 413, 415, 421-
Arm contribution 56 422, 424, 429, 436
Asymptotic symmetry 419 Fluctuations
Austenite 252, 284, 286 order parameter 402
Birman criterion 74 HN 2 43, 77, 88

Burnside's theorem 111 Hysteresis 216
CeAh 334 IR see Irreducible representation

Chaotic structure 321-322 IRBI see Integral rational basis of
Correlation invariants
order parameter fluctuations 402 Icosahedral symmetry 372
Correlation length 402, 412, 437 I-group 118, 417
Critical indices 402-404,412,415- Inhomogeneous phase (structure)
416,421,436 301-302, 340
Critical space dimension 436 Initial phase 7
Curie principle 82 Integral rational basis of invariants
(IRBI) 104, 112, 114
Devil's staircase 329,331, 353, 355 minimal (MIRBI) 111
Dissymmetric phase 7,74,77,156, Irreducible representation (IR) 7
160, 172, 212 Isostructural transition 143
Domains 84-86, 336
antiphase 86, 246 K 2IrCl6 422
arm 85,91,202,246 KMnF 3 173,199
orientational 85, 88, 202 KSe04 347
Domain wall 278, 282, 286, 300,
Lifschitz invariants 304, 341, 345,
320
347
DyC 2 422
Lock-in transition 353
Exchange group 359, 361
MIRBI see Minimal integral ratio-
FeGe2 360, 362 nal basis of invariants
441
442 INDEX
Martensite 253, 284, 286 Paraphase 91, 94

Mixing coefficients 76 Penrose tilings 374
MnAhSi0 12 47, 356 Permutation representation 23
MnAs 117, 170 Phase diagrams 131,144,150,155,
Mode 161,170,171,215,310,315,
displacement 37 317,331,340
magnetic 46 Phase transition
permutation 29 ferroelectric 168
strain 192, 196, 216, 268 improper 198, 204, 234
Multidimensional group 366, 369 magnetic 168, 171
Multi-K-structure 332, 334, 336 martensitic 252, 255-257
order-disorder 29, 31
Nb-I1 30, 88 orientational 179, 227
Nb0 2 419 proper 192, 204, 209, 233
Nb 3 S4 38, 77, 88, 223 pseudoproper 198, 238
Nd 336 reconstructive 250
(NH 4hS04 94, 239, 244 structural 168, 171
Noether's theorem 112 superconducting 390-391
Nucleus 287, 292, 297 Phason 330
Point
OP see Order parameter
bicritical 427, 430
Omega phase 292 Lifschitz 302, 316, 434, 436-437
One-ion anisotropy group 364 quadrupole 225
Orbit 24 tetracritical 226, 427, 430
Order parameter (OP) tricritical 222, 432
concomitant 178
coupled 168, 171, 197,430-431 Quasicrystals 373
macroscopIC 18, 182, 188, 216,
Region
266
existence of phases 158, 160,221
magnetic 47,168,171,182
Renormalization group 408
microscopic 17,38,43,47
multicomponent 148, 152, 161, Shape memory effect 274
171,179,222,419 Shubnikov group 358, 362
quantum mechanical 390 Soliton lattice 318,321,323
structural 38,43,171,199 Stability
superconducting 390-391 dissymmetric phase 1:38,151, 154,
Ordered phase 27, 29 157, 159, 162,221
Orientational relations 250 initial phase 133, 149
INDEX 443
potential 134, 318, 333, 416 Transition channel 61

Stabilizer 24
Universal classes 123, 416
Susceptibility 206, 216, 233, 239,
353 Vector representation 36
V3 Si 38, 77, 88, 223
Ta-H 30,88
TbAs 423 Wave-vector 13
TbAu2 422
TbP 423 ZnCrSe4 359
TbSb 423 ZrV 2 43,77,88

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Phase Transitions and Crystal Symmetry

Fundamental Theories of Physics

An International Book Series on The Fundamental Theories of Physics:

Editor: ALWYN V AN DER MERWE

Editorial Advisory Board:

Published by Kluwer Academic Publishers,

Kluwer Academic Publishers incorporates

Sold and distributed in the U.S.A. and Canada

In all other countries, sold and distributed

Printed on acid-free paper

This is the expanded and revised translation of the original work

Translated from the Russian by A.P. Zavarnitsyn

All Rights Reserved

No part of the material protected by this copyright notice may be reproduced or

Preface to the English Edition XVll

Chapter 1. Introduction to Phenomenological Phase Transition

Chapter 2. Physical Realization of the Order Parameters at a Micro-

5. Vector Representation and its Basis . . . . . . . . . . . . . . . 36

Chapter 3. Symmetry Change at Phase Transitions 52

Chapter 4. Analysis of the Thermodynamic Potential 100

in A-15 compounds (114). Constructing the IRBI for the structural

Chapter 5. Phase Diagrams in the Space of Thermodynamic

model (156). Cubic invariants in the 1]6 model (159).

Chapter 6. Macroscopic Order Parameters 188

Chapter 7. Phase Transitions in an External Field 215

29. Domains in an External Field . . . . . . . . . . . . . . . . . 244

Chapter 8. Martensite Transformations 250

Chapter 9. Incommensurate Periodicity Phases 301

37. Multi-K-structures 332

Chapter 10. Color Symmetry and its Role in Phase Transition

symmetry group (391). OP symmetry and the behavior of the gap

Chapter 11. Fluctuations and Symmetry 404

A special challenge to the authors was the exposition of methods that

of specific structures. Consideration is given also to another aspect of color

G crystal space group

r coefficient of a quadratic expansion term

Introduction to Phenomenological Phase

1. Fundamentals of Landau's Thermodynamic Theory

ELEMENTARY THERMODYNAMIC ANALYSIS

The equilibrium value of the OP is determined from the requirement that

We adduce the major arguments of Landau's theory: For the equilibrium

l' = r~(T - To) + .... (1.4)

We start by considering the case where the coefficient v is identically equal

whence it follows that two real-valued solutions of this equation exist: 7} =0

Fig. 1.1. Thermodynamic potential in the vicinity of the second-order

r ::; 9v 2 /32u. (1.10)

These solutions as a function of r, that is, temperature, are presented in Fig.

Fig 1.3. Solutions to the equation of state (1.8) in the presence of

The ambiguous behavior ofthe OP in the temperature range corresponding

The analysis performed applies to a phase transition that is character-

SPONTANEOUS SYMMETRY BREAKING AT A CONTINUOUS PHASE TRANSITION

Each low-symmetry phase will be called a dissymmetric phase and de-

where CX is an expansion coefficient which is independent of coordinates but

coefficients CA and may be written in the form

<1> = <1>0 + 2:>'v L(CA)2 + .... (1.20)

The corresponding IR D V is said to be responsible for the phase transition.

<1> = <1>0 + r L 1]X + ... , (1.22)

8p(r) = L 1]A9;\(r). (1.23)

THE LANDAU CONDITION FOR A SECOND-ORDER PHASE TRANSITION