Crystal field

Theory
 CoNtents
Crystal field theory
1. Introduction
2. Postulates of crystal field
theory
3. Crystal field splitting in
octahedral coordination
entities
4. Crystal field splitting in
tetrahedral coordination
entities
5. Colours In coordination
compounds
6. Limitations
7. Bibliography
 Crystal field
theory
Introduction
CFT was developed by physicists Hans
Bethe[1] and John Hasbrouck van
Vleck[2] in the 1930s. CFT was
subsequently combined with
molecular orbital theory to form the
more realistic and complex ligand field
theory (LFT), which delivers insight
into the process of chemical bonding
in transition metal complexes.
Postulates of the crystal field
theory

 The crystal field theory (CFT) is

an electrostatic model which
considers the metal-ligand bond to
be ionic arising purely from
electrostatic interactions between
the metal ion and the ligand.

 Ligands are treated as point

charges in case of anions or point
dipoles in case of neutral
molecules.

 The five d orbitals in an isolated

gaseous metal atom/ion have same
energy, i.e., they are degenerate.
This degeneracy is maintained if a
spherically symmetrical field of
negative charges surrounds the
metal atom/ion. However, when
this negative field is due to ligands
(either anions or the negative ends
of dipolar molecules like NH3 and
H2O) in a complex, it becomes
asymmetrical and the degeneracy
of the d orbitals is lifted. It results
in splitting of the d orbitals. The
pattern of splitting depends upon
the nature of the crystal field. Let
us explain this splitting in different
crystal fields.
  Crystal field splitting in
octahedral coordination entities

In an octahedral coordination entity

with six ligands surrounding the metal
atom/ion, there will be repulsion
between the electrons in metal d
orbitals and the electrons (or negative
charges) of the ligands. Such a
repulsion is more when the metal d
orbital is directed towards the ligand
than when it is away from the ligand.
Thus, the dx²-y² and dz² orbitals which
point towards the axes along the
direction of the ligand will experience
more repulsion and will be raised in
energy; and the dxy , dyz and dxz
orbitals which are directed between
the axes will be lowered in energy
relative to the average energy in the
spherical crystal field. Thus, the
degeneracy of the d orbitals has been
removed due to ligand electron-metal
electron repulsions in the octahedral
complex to yield three orbitals of
lower energy, t2g set and two orbitals
of seen higher energy , eg set. This
splitting of the degenerate levels due
to the presence of ligands in a definite
geometry is termed as crystal set.
This splitting of the degenerate levels
due to the presence of ligands in a
definite geometry is termed as crystal
field splitting and the energy
separation is denoted by ∆o(the
subscript o is for octahedral). Thus,
the energy of the two eg orbitals will
increase by (3/5) ∆o and that of the
three t2g will decrease by (2/5) ∆o .
The crystal field splitting, (∆o),
depends upon
the field produced by the ligand and
charge on the metal ion. Some ligands
are able to produce strong fields in
which case, the splitting will be large
whereas others produce weak fields
and consequently result in small
splitting of d orbitals. In general,
ligands can be arranged in a series in
the order of increasing field strength
as given below:

I– < Br– < SCN– < Cl– < S2– < F– < OH–
< C2 O4 2– < H2O < NCS –< edta4– <
NH3 < en < CN– < CO

Such a series is termed as

spectrochemical series. It is an
experimentally determined series
based on the absorption of light by
complexes with different ligands .

Let us assign electrons in the d

orbitals of metal ion in octahedral
coordination entities. Obviously, the
single d electron occupies one of the
lower energy t2g orbitals. In d2 and d3
coordination entities, the d electrons
occupy the t2g orbitals singly in
accordance with the Hund’s rule. For
d4 ions, two possible patterns of
electron distribution arise:
(i) the fourth electron could either
enter the t2g level and pair with an
existing electron, or (ii) it could avoid
paying the price of the pairing energy
by occupying the eg level. Which of
these possibilities occurs, depends on
the relative magnitude of the crystal
field splitting, ∆o and the pairing
energy, P (P represents the energy
required for electron pairing in a
single orbital). The two options are:
(i) If ∆o < P, the fourth electron enters
one of the eg orbitals giving the
configuration t2g3eg1 . Ligands for which
∆o < P are known as weak field
ligands and form high spin complexes.
(ii) If ∆o > P, it becomes more
energetically favourable for the fourth
electron to occupy a t2g orbital with
configuration t2g 4eg 0. Ligands which
produce this effect are known as
strong field ligands and form low spin
complexes.
  Crystal field splitting in
tetrahedral coordination entities

In tetrahedral coordination entity

formation, the d orbital splitting is
inverted and is smaller as compared
to the octahedral field splitting. For
the same metal, the same ligands and
metal-ligand distances, it can be
shown that ∆t = (4/9) ∆0 .
Consequently, the orbital splitting
energies are not sufficiently large for
forcing pairing and, therefore, low spin
configurations are rarely observed.
The ‘g’ subscript is used for the
octahedral and square planar
complexes which have centre of
symmetry. Since tetrahedral
complexes lack symmetry, ‘g’
subscript is not used with energy
levels.
D orbital splitting in a
tetrahedral crystal field
 Colour in Coordination Compounds

We learnt that one of the most

distinctive properties of transition
metal complexes is their wide range of
colours. This means that some of the
visible spectrum is being removed
from white light as it passes through
the sample, so the light that emerges
is no longer white. The colour of the
complex is complementary to that
which is absorbed. The
complementary colour is the colour
generated from the wavelength left
over; if green light is absorbed by the
complex, it appears red.
Table below gives the relationship of
the different wavelength absorbed
and the colour observed.
Examples of colour in coordination
compounds

The colour in the coordination

compounds can be readily explained
in terms of the crystal field theory.
Consider, for example, the complex
[Ti(H2O)6]3+, which is violet in colour.
This is an octahedral complex where
the single electron (Ti3+ is a 3d1
system) in the metal d orbital is in the
t2g level in the ground state of the
complex. The next higher state
available for the electron is the empty
eg level. If light corresponding to the
energy of blue-green region is
absorbed by the complex, it would
excite the electron from t2g level to the
eg level (t2g 1eg 0 – t2g 0eg 1).
Consequently, the complex appears
violet in colour . The crystal field
theory attributes the colour of the
coordination compounds to d-d
transition of the electron.
It is important to note that in the
absence of ligand, crystal field
splitting does not occur and hence the
substance is colourless. For example,
removal of water from [Ti(H2O)6 ]Cl3 on
heating renders it colourless.
Similarly, anhydrous CuSO4 is white,
but CuSO4 .5H2O is blue in colour. The
influence of the ligand on the colour of
a complex may be illustrated by
considering the [Ni(H2O)6 ]2+ complex,
which forms when nickel(II) chloride is
dissolved in water. If the didentate
ligand, ethane-1,2 diamine(en) is
progressively added in the molar
ratios en:Ni, 1:1, 2:1, 3:1, the
following series of reactions and their
associated colour changes occur:
  Aqueous solutions of complexes
of nickel(II) with an increasing
number of ethane-1, 2-diamine
ligands.
Limitations of crystal field theory

The crystal field model is successful in

explaining the formation, structures,
colour and magnetic properties of
coordination compounds to a large
extent. However, from the
assumptions that the ligands are point
charges, it follows that anionic ligands
should exert the greatest splitting
effect. The anionic ligands actually are
found at the low end of the
spectrochemical series. Further, it
does not take into account the
covalent character of bonding
 between the ligand and the central
atom. These are some of the
weaknesses of CFT, which are
explained by ligand field theory (LFT)
and molecular orbital theory which are
beyond the scope of the present
Bibliography
 Chemistry textbook for class 12
(2024-25 edition )
 Wikipedia
 www.scribd.com
 Google.com
 Internet