Indian J Phys

DOI 10.1007/s12648-016-0887-9

ORIGINAL PAPER

Probing structural distortions in rare earth chromites using Indian

synchrotron radiation source
R Late1, H M Rai2, S K Saxena2, R Kumar2, A Sagdeo3 and P R Sagdeo2*
1

Department of Physics, Ahmednagar College, Ahmednagar, Maharashtra 414001, India

Material Research Laboratory, Discipline of Physics and Centre for Material Science and Engineering, Indian Institute of Technology Indore,
Khandwa Road, Simrol, M.P. 452020, India
3

Indus Synchrotron Utilization Division, Raja Ramanna Center for Advanced Technology, Indore, M.P. 452013, India
Received: 11 April 2016 / Accepted: 30 May 2016

Abstract: Effect of R site ionic radius on the structural distortions in RCrO3 (R: La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er,
Yb and Y) rare earth perovskite chromites is investigated through synchrotron based X-ray diffraction technique. The said
structural distortions are measured in the terms of CrO bond lengths, CrO6 octahedral tilt, tolerance factor (t) and RO12
polyhedral distortion. It is observed that the lattice parameters (b and c), RO bond length, tolerance factor and CrOCr
bond angle increases with increase in the radius of R site ion; whereas octahedral tilts (along [010] and [101]) and RO12
polyhedral distortion decreases with increase in the radius of R site ion. Further it is observed that the radius of R site cation
does not have significant effect on lattice parameter a and CrO bond length (hence on the distortion of CrO6 octahedra). A
comparison of the crystal structure parameters obtained using refinement of synchrotron powder X-ray data and that
estimated theoretically using modern bond valence parameters (SPuDS) has been carried out. A one to one correlation
between the experimental and theoretical results has been observed.
Keywords: X-ray diffraction; Synchrotron radiation; Crystallography
PACS Nos.: 61.10.Nz; 41.60.Ap; 61.90.?d

1. Introduction
The ABO3 type perovskite oxides are very important from
fundamental and technological point of view [1, 2]. These
perovskite structures are characterized by Glazer tilts and
distortions associated with BO6 octahedra. The said Glazer
tilts and distortions can be tuned by external perturbations
such as temperature, pressure etc. [3, 4] and these distortions are known to control various physical properties (such
as ferroelectric, electrical, optical and magnetic) of these
perovskite oxides [1, 2]. Hence it is very important and
sometimes very crucial to determine these structural
parameters with a great accuracy [5, 6]. Due to the presence of low Z element i.e. oxygen in perovskite oxides
the measured values of BO bond lengths and tilts associated with BO6 octahedra may have large errors. This is

due to low value of atomic scattering factor associated with

oxygen (in case the diffraction data is collected using low
power X-ray lab source). The neutron diffraction measurements or highly intense (high flux) synchrotron based
diffraction measurements may be useful in this regard. In
the present study we have systematically studied rare earth
chromites using synchrotron X-ray diffraction experiments
and have estimated the above mentioned tilts and bond
lengths associated with CrO6 octahedra and compared the
obtained results with theoretical results. A one to one
correlation between the experimental and theoretical result
has been observed.
The rare earth perovskite chromites with generic formula RCrO3 (R: La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er,
Yb and Y) generally crystallizes in orthorhombic structure
(Space group Pnma). In these samples chromium (Cr3?) is
JahnTeller inactive ion and crystal structure is centrosymmetric, hence out of all the possible distortions, the
collective rotations (tilts) of the CrO6 octahedra is of

*Corresponding author, E-mail: prs@iiti.ac.in

2016 IACS

R Late et al.

particular importance. The collective rotations (tilts) of the

CrO6 octahedra for Pnma setting are commonly indexed in
Glazer tilting scheme as a b a [3, 5]. Another
parameter which characterizes the degree of distortion
from ideal perovskite structure commonly known as
Goldschmidtspgeometrical
tolerance factor (t) is given by

t rR ro = 2rCr ro , where rR , rCr , rO are ionic

radii of rare earth (R3?) cation, chromium cation (Cr3?)
and oxygen anion (O2-) respectively. For the ideal cubic
perovskite structure the value of t is 1. For distorted perovskite type structure t generally takes the range of
0:7 [ t \ 1:1 [7, 8]. It is also well known in perovskite
oxides that the most of the properties of perovskite oxide
are significantly altered by BOB bond length, bond angle
and BO orbital overlap [2]. Hence variation of the octahedral rotation by varying ionic radii of R (chemical
pressure) is an effective way to modify the structural and
various other properties of perovskite oxide.
Recently rare earth chromites have attracted considerable interest due to their multiferroic properties, spontaneous ferroelectricity, interesting magnetic and dielectric
properties [922]. However, whole series of rare earth
chromites RCrO3 (R: La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho,
Er, Yb and Y) have rarely been explored for structural
distortions using synchrotron radiation experiments.
Keeping this in view in the present study details of structural distortions in RCrO3 as a function rare earth cation
size by means of Reitveld refinement using synchrotron
X-ray diffraction data has been discussed.

3. Results and discussion

Figure 1(a) shows the representative refined powder
diffraction pattern obtained for SmCrO3. All the compounds from LaCrO3 to YbCrO3 are indexed using
orthorhombic crystal structure with space group Pnma
[27]. A polynomial with six parameters is fitted to
background and pseudo-voigt function is used to generate the peak shape of the diffraction data. The lattice
parameters obtained from the refinements considering
Pnma setting for all the compounds are shown in
Fig. 1(b). In order to understand the effect of R site
ionic radius on various structural distortions such as
glazer tilt, we have used the refined lattice parameters to
find the distortions along (101) and (010) axis of basic

2. Experimental details
Polycrystalline samples of RCrO3 (R: La, Pr, Nd, Sm, Eu,
Gd, Tb, Dy, Ho, Er, Yb and Y) were prepared by conventional solid-state reaction route. The stoichiometric
amount of starting materials Cr2O3 and corresponding rare
earth oxide or yttrium oxide of 99.99 % purity were mixed
and milled with 2-propanol in Agate-mortar for 45 h. The
resulting homogenous mixture was calcined up to 1300 C
for 48 h with intermediate grindings. In order to examine
the phase purity and crystal structure of the prepared
samples, powder X-ray diffraction (XRD) experiments
were carried at BL-12 ADXRD beamline at Indus-2 synchrotron radiation source. The energy of the incidence
X-ray beam was 15 keV. The diffraction pattern was
recorded in the 2h range of 1060 with step size of 0.01,
using Huber six circle diffractometer (model: 5020). More
technical details about the ADXRD beamline are reported
elsewhere [23, 24]. All obtained diffraction patterns were
analyzed using the FullProf suite [25] and VESTA software
[26] was used for visualization of the refined crystal
structure and to measure the tilt angle bond lengths.

Fig. 1 (a) Rietveld refined Powder X ray Diffraction for SmCrO3,

inset shows the quality of fit with Wyckoff positions used for
refinement, (b) variation of lattice parameters with rare earth cationic
radii derived from Rietveld refined powder X ray diffraction for all
synthesized RCrO3 compounds

Probing structural distortions in rare earth chromites

cubic perovskite structure based on the formalism proposed by Zhao et al. [28]. The schematic for the various
octahedral rotation angles observed in ideal cubic ABO3
type perovskite, shown as rotation h along (101) and u
along (010) etc. are shown in Fig. 2(a). Zhao et al. [28]
have proposed that the octahedral rotation angles h
along [101] and u along [010] can be calculated as
follows
c
p c 
h cos1
and / cos1 2
1
a
b
Here a, b and c are the lattice parameters of orthorhombic
unit cell. Further, it is also known that distortion in
perovskite can be described only by the three fold axes
(111), of regular octahedral. This angle can be calculated
from unit cell dimensions as follows

(a)

(111)

(010)

A
B
O

(101)

(b)

Fig. 2 (a) Schematic view of the crystal structure of ideal cubic

perovskite ABO3 showing the octahedral rotation h along (101) and /
(010) and result of tilting A (111) axes of regular octahedra,
(b) variation of octahedral tilt along / (010) and h (101) pseudocubic
axes with the rare earth cation ionic radii for all compounds

U cos1

p 2 
2c
ab

and

cos U cos h cos u

The variation of rotation angles derived from

orthorhombic crystal structure using above formalism is
shown in Fig. 2(b). It is observed that the octahedral tilt
distortions (/ and h) decreases within the series, with
increase in ionic radii of R site ion.
It should be noted that in the case of ABO3 type perovskite oxides the overlap between the f-orbital of rare
earth cation and oxygen 2p anion (RO bond length) and
similarly overlap between Cr-3d and oxygen-2p orbitals
(CrO bond length) plays a very crucial role in deciding
various properties of perovskite oxides. Hence in order to
understand the effect of ionic radius of R-site ion on RO
and CrO bond length, we have used the refined Wyckoff
positions of R, Cr, O and calculated variations of the
average bond distances RO (for 12 and 9 coordination)
and CrO (6 coordination). Here we have used two different averaging methods, arithmetic mean (AM) and
geometric mean (GM). AM and GM averaging of CrO
bonds produce similar values in case of CrO bond lengths.
On the other hand for RO12 polyhedra, GM produces
smaller average magnitude of bond length; this might be
due to the fact that GM puts less weight on longer bonds
[29]. The variation of (average values) CrO and RO
bond lengths are shown in Fig. 3 and the details of various
bond lengths are listed in Table 1. The fractional values of
Wyckoff positions along with estimated standard deviation
(figures in bracket) as estimated using Fullprof are given in
Table 2. From Table 1 it is clearly observed that in the
distorted structure of RCrO3 the individual RO bonds
show very large differences in magnitude. This might be

Fig. 3 Variation of average RO and CrO bond length calculated

from Refinement output parameter, inset shows the variation of
experimentally observed bond angle with ionic radii of rare earth
cation

GM

AM

GM

AM

GM

AM

GM

AM
GM

AM

GM

t9

RO D12

RO D12

CrO D6

CrO D6

RO D9

RO D9

(R3?)9
(R3?)9

(R3?)12

(R3?)12

2.711

1.351

1.362

1.243
1.311

3.920

3.463

0.000

0.000

8.074

7.995

0.971

0.947

GM

AM

t9

2.643

AM

9 coordination
average RO

1.973
0.990
0.986

AM
GM

GM

2.751

GM
1.973

2.762

AM

AM

5.522 (6)

5.486 (2)
7.768 (5)

a
b

LaCrO3

Lattice
parameter

t12
t12

6 coordination
average CrO dist

12 coordination
average RO dist

Compound

1.341

1.360

1.203
1.278

6.924

6.489

0.000

0.000

14.494

14.245

0.956

0.929

2.678

2.603

0.985
0.978

1.982

1.982

2.741

2.760

5.463 (5)

5.490 (6)
7.733 (1)

PrCrO3

1.334

1.355

1.189
1.262

7.790

7.434

0.029

0.029

16.478

16.160

0.951

0.924

2.662

2.589

0.984
0.976

1.980

1.981

2.734

2.755

5.429 (1)

5.492 (8)
7.704 (7)

NdCrO3

1.326

1.353

1.161
1.244

9.152

8.701

0.011

0.011

20.935

20.430

0.943

0.913

2.644

2.561

0.982
0.972

1.983

1.983

2.726

2.753

5.377 (7)

5.512 (5)
7.660 (1)

SmCrO3

Table 1 Various structural parameters derived from the Reitveld refined output data

1.322

1.351

1.146
1.234

9.401

8.877

0.018

0.018

23.157

22.545

0.939

0.908

2.634

2.546

0.981
0.971

1.983

1.983

2.722

2.751

5.349 (7)

5.522 (2)
7.637 (3)

EuCrO3

1.320

1.354

1.134
1.227

10.333

9.758

0.024

0.024

26.076

25.305

0.935

0.902

2.627

2.534

0.980
0.968

1.988

1.988

2.720

2.754

5.327 (1)

5.535 (6)
7.623 (8)

GdCrO3

1.311

1.345

1.120
1.212

9.386

8.742

0.087

0.086

26.684

25.884

0.932

0.899

2.612

2.520

0.980
0.968

1.981

1.982

2.711

2.745

5.302 (1)

5.525 (1)
7.588 (7)

TbCrO3

1.308

1.345

1.114
1.215

11.891

11.252

0.051

0.051

29.307

28.341

0.931

0.895

2.615

2.514

0.977
0.964

1.986

1.986

2.708

2.745

5.279 (8)

5.530 (9)
7.573 (1)

DyCrO3

1.303

1.345

1.098
1.202

13.254

12.656

0.035

0.035

33.514

32.261

0.923

0.886

2.602

2.498

0.974
0.959

1.994

1.994

2.703

2.745

5.257 (1)

5.528 (1)
7.555 (1)

HoCrO3

1.303

1.343

1.101
1.202

11.822

11.165

0.045

0.045

31.430

30.327

0.927

0.891

2.602

2.501

0.976
0.962

1.986

1.986

2.703

2.743

5.257 (9)

5.532 (1)
7.554 (2)

YCrO3

1.299

1.340

1.097
1.202

12.678

11.985

0.101

0.101

32.424

31.251

0.926

0.889

2.602

2.497

0.975
0.961

1.987

1.987

2.699

2.740

5.240 (9)

5.529 (1)
7.542 (1)

ErCrO3

1.287

1.331

1.081
1.190

13.859

13.160

0.044

0.044

34.701

33.362

0.924

0.885

2.590

2.481

0.974
0.959

1.983

1.983

2.687

2.731

5.205 (3)

5.511 (5)
7.502 (7)

YbCrO3

R Late et al.

-0.3065 (2)

0.0556 (4)
0.0522 (1)

-0.3063 (1)
-0.3059 (3)

0.0538 (2)
0.0562 (1)

-0.3083 (2)
-0.3010 (1)

0.0521 (3)
0.0506 (1)

-0.3059 (2)
-0.3014 (6)

0.0500 (5)
0.0472 (1)

-0.2975 (1)
-0.2963 (1)

0.0459 (3)
0.0417 (2)

-0.2896 (5)

0.0345 (3)

-0.2730 (5)

0.0399 (2)

due to the fact that the different electrons (planar and axial)
from f-orbitals take part in bonding and these bond lengths
are found to be split into three groups: six short bonds,
three medium length bonds and three long bonds (12
coordinated). A large variation in the values of bond distances makes the rare earth coordination number with
respect to oxygen anion uncertain. The inset of Fig. 3
shows the variation in CrOCr bond angle as a function of
ionic radius of R-site ion. From Fig. 3 it is clear that Cr
OCr bond angle systematically increases with ionic radius
(it should be noted that for ideal cubic perovskite system
the CrOCr bond angle should be 180), whereas CrO
bond length almost remains constant.
As the value of tolerance factor t is known to play very
crucial role in deciding various properties of these perovskite oxides [30]. Hence, based on AM and GM averaging,
we calculate the tolerance factor (t12 and t9) for 12 and 9 fold
coordination and compare them with the tolerance factor
calculated using other methods such as calculated from ionic
radii of individual cation and anion [31]. The results of the
tolerance factor calculated from 9 coordinated RO bonds
are found to have close match with those reported literature
[27]. Using the average values of bond lengths we have
estimated the ionic radius of R site cations for 12 and 9
coordination {(R3?)12 and (R3?)9} and have compared the
same with available literature [32]. The observed value of
ionic radius matches closely with those calculated using the
empirical formula proposed by Jia [32].
In order to further quantify the relative distortion of the
polyhedra and deviation from ideal perovskite structure
[33] we determine bond length distortion parameter (D)
given below by Eq. (3).

-0.2877 (6)

0.1138 (7)

0.3043 (6)
0.3066 (3)

0.1081 (1)
0.1005 (1)

0.3028 (2)
0.3047 (7)

0.1056 (1)
0.1028 (2)

0.3006 (3)
0.3001 (1)

0.0853 (1)
0.0918 (1)

0.2960 (4)
0.2957 (1)

0.0874 (1)
0.0866 (6)

0.2929 (6)
0.2921 (3)

0.0798 (1)
0.0786 (2)

0.2872 (6)

0.0650 (4)

0.2732 (7)

x
O2

0.25000

0.4638 (6)
0.4662 (5)

0.25000
0.25000

0.4648 (1)
0.4622 (2)

0.25000
0.25000

0.4680 (1)
0.4724 (5)

0.25000
0.25000

0.4667 (1)
0.4712 (2)

0.25000
0.25000

0.4764 (2)
0.4838 (3)

0.25000
y

0.4838 (6)

0.25000

0.4935 (2)
x
O1

0.50000
0.50000

0.25000

0.00000

0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000
0.50000

0.00000

0.00000
0.00000

0.50000

0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000

-0.0188 (1)

0.00000

0.00000

-0.0181 (1)
-0.0170 (2)

0.00000
0.00000

-0.0165 (3)
-0.0159 (1)

0.00000
0.00000

-0.0147 (5)
-0.0143 (1)

0.00000
0.00000

-0.0129 (3)
-0.0115 (1)

0.00000
0.00000
0.00000
Cr

0.00000

-0.0069 (1)
-0.0041 (3)
z

-0.0084 (2)

0.25000

0.0693 (2)
0.0666 (8)

0.25000
0.25000

0.0660 (9)
0.0657 (2)

0.25000
0.25000

0.0636 (3)
0.0621 (2)

0.25000
0.25000

0.0588 (3)
0.0552 (3)

0.25000
0.25000

0.0508 (8)
0.0418 (2)

0.25000
0.25000
y

0.0356 (5)

0.25000

0.0190 (5)
x
R

YbCrO3
ErCrO3
YCrO3
HoCrO3
DyCrO3
TbCrO3
GdCrO3
EuCrO3
SmCrO3
NdCrO3
PrCrO3
LaCrO3
Positi-on
Atom

Table 2 Wyckoff positions and estimated standard deviation (values in bracket) determined from Reitveld refinement data of all studied rare earth chromite compounds using Fullprof suit

Probing structural distortions in rare earth chromites

Fig. 4 Variation of polyhedral distortion D12 for RO12 polyhedra and

D6 for CrO6 octahedra with the rare earth cation ionic radii for all the
compounds

R Late et al.


n 
103 X
di  d 2
Dn
d
n i1

where di . and d are individual and average inter-atomic

distances with coordination number n. The bond length
distortion parameter have been calculated for 12 and 9
coordination of R cation and 6 coordination for Cr cation
by above mentioned averaging methods. From the calculated values, we have found that CrO6 octahedra is almost
un-distorted for all the studied samples, on the other hand
RO12 polyhedra is more distorted. The variation of polyhedral distortion for RO D12 and CrO D6 is shown in Fig. 4.
As the distortion of the CrO6 octahedra is found to be
very small, hence it is possible and justified to use the
structure prediction diagnostic software (SPuDS) [34] to
verify the observed experimental results. SPuDS initially

Fig. 5 Comparative variations of experimentally observed (solid

symbols) and theoretically generated (open symbol) parameter
(a) average CrOCr bond angle and (b) Average RO and CrO
bond lengths

consider the CrO6 octahedra to remain rigid. This seems to

be reasonable as most distorted perovskites have a small
distortion in bond length. The same is experimentally
observed for the present case (see Fig. 4). With this
restriction the full crystal structure may be predicted considering the size of the octahedron and the magnitude of the
octahedral tilting. In case R site cation does not have a
fixed Wyckoff position then one may need to consider
additional degrees of freedom which are part of the SPuDS
calculations. The size of the octahedron (considering bond
length) and the magnitude of the octahedral tilts are calculated using bond valence sum rule proposed by I.
D. Brown [35]. Figs. 5(a) and 5(b) show the comparative
graphs obtained experimentally (solid symbols) and generated theoretically (open symbol) using SPuDS. The one
to one correlation between the experimental and theoretical
patters is clearly evident; suggesting the validity of the
various crystal structure parameters obtained from the
experimental data.
As already discussed in the introduction, recently; rare
earth chromites have attracted considerable interest due to
their multiferroic properties [922]. It is well known that in
order to have spontaneous electric polarization, the crystallographic structure must be non-centrosymmetric;
whereas the present analysis suggests that the global
structure of all the studied samples at room temperature
appears to be centrosymmetric. A systematic extended

Fig. 6 (a) Variation of ferroelectric transition temperature TFE and

antiferromagnetic Neel temperature TN as a function of radius of R
site ion. (b) Variation of structural distortion parameter such as
tolerance factor (t) and polyhedral distortion as a function of ionic
radius of rare earth ion

Probing structural distortions in rare earth chromites

Table 3 Various structural distortion parameters deduced from this study and transition temperatures (antiferromagnetic TN and ferroelectric
TFE) of various studied compounds taken from literature
Compound

Ionic radius (pm)

Tolerance factor (t)

LaCrO3

116.0

0.971

PrCrO3

112.6

NdCrO3

110.9

SmCrO3

Polyhedral distortion (RO D12)

TN (K)

TFE (K)

8.074

288 [36]

Non-ferroelectric [19]

0.956

14.494

239 [36]

Non-ferroelectric [36]

0.951

16.478

226 [36]

Non-ferroelectric [36]

107.9

0.943

20.935

193 [11, 36]

220 [11]

EuCrO3

106.6

0.939

23.157

185 [36]

Not available

GdCrO3

105.3

0.935

26.076

171 [36]

Not available

TbCrO3
DyCrO3

104.0
102.7

0.932
0.931

26.684
29.307

159 [36]
149 [36]

446 [37]
530 [38]

YCrO3

101.9

0.927

31.430

141 [36]

473 [21, 36]

HoCrO3

101.5

0.923

33.514

142 [36]

474 [36]

ErCrO3

100.4

0.926

32.424

136 [36]

477 [36]

YbCrO3

098.5

0.924

34.701

120 [36]

503 [36]

X-ray absorption fine structural studies or temperature

dependent X-ray diffraction studies across the observed
transition temperatures may be useful in this regard.
In order to understand the magnetic and ferroelectric
phase diagram available in literature [19, 36, 37] with
respect to the presently estimated structural parameters we
have reconstructed phase diagram and same is represented
as Fig. 6. The corresponding values of transition temperatures taken from literature [19, 36, 37] are tabulated in
Table 3. The phase diagram [Fig. 6(a)] indicates various
regions like AFM (antiferromagnetic), FE (ferroelectric),
PM (paramagnetic) ? FE and PM ? PE (paraelectric). It
can be observed that the AFM Neel temperature TN
increases with increase in the radius of the rare-earth ion
[represented by blue dotted band in Fig. 6(a)] while the
ferroelectric transition temperature TFE decreases with
increase in the ionic radii, further the RCrO3 chromites
with ionic radius of R-site ion greater than 108 pm are nonferroelectric in nature [19, 36], it is represented by red
dotted band in Fig. 6(b). Further comparing Figs. 6(a) and
6(b), it appears that the compounds with tolerance factor
(t) less than 0.943 and polyhedral distortion greater than
20.935 may show ferroelectricity with magnetic ordering
which needs to be further explored by means of multisite
and multiple element doping.

4. Conclusions
In conclusion we have prepared high quality single phase
samples of RCrO3 perovskite oxides with R = La, Pr, Nd,
Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb and Y. The synchrotron
powder X-ray diffraction measurements have been carried
out on all the samples. Our results and analysis suggest that
the RCrO3 system crystallizes in orthorhombic structure

with space group Pnma. Further, the comparison of tolerance factor calculated considering the ionic radius and
bond length, suggests that the tolerance factor calculated
using bond length appears to be more accurate as compared
to that calculated using ionic radius. The calculation of the
bond lengths considering arithmetic mean and geometric
mean suggests that geometric mean approach is more
appropriate for higher ionic radii rare earth compounds. A
one to one correspondence between the experimental and
theoretical calculations confirms the validity of the various
crystal structure parameters obtained for the experimental
diffraction data.
Acknowledgments Authors sincerely thank Raja Ramanna Center
for Advanced Technology (RRCAT) Indore for providing synchrotron
radiation facilities. Authors are thankful to Dr. A. K. Sinha, Mr. Anuj
Upadhyay and Mr. Manvendra N. Singh for their help during X-ray
diffraction measurements. One of the authors (RL) acknowledges
MHRD, India for providing financial support in the form of Teaching
Assistantship. CSIR, New Delhi is acknowledged for funding high
temperature furnace under the Project 03(1274)/13/EMR-II used for
the sample preparations.

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