Unit 1

B.Tech Module No 1.3

Crystal Field Theory

The VBT does not explain i) the colour and ii) the spectra, of the
complexes. And also it does not explain why the magnetic moment
changes as the temperature changes. The crystal field theory is much more
widely used than the valence bond theory. The model that largely replaced
valence bond theory for interpreting the chemistry of coordination
compounds was the crystal field theory. This theory was first proposed by
Hans Bethe (1929) and modified by J.H. van Vleck (1935). This theory is
also known as ligand field theory.

Pure crystal field theory assumes that the only interaction between the
metal ion and the ligands is an electrostatic or ionic force. The central metal
atom or the ion and the ligands in the complex are considered as point
charges. Then the bonding in a complex may be ion ion attractions (i.e.
between a cation and negative ions). Also the ion dipole attractions may
give rise to bonding. (If the ligand is a neutral molecule such as NH3 and
H2O etc). For example NH3 has a dipole moment. In this molecule N H


bond has the polarities . This theory is successful in interpreting
N
H
many important properties of complexes. Symmetry considerations
involved in this theory are identified with those of the molecular orbital
theory.
To understand this theory properly, one should have clear idea of the
geometries of the d orbitals in an atom. There are five d orbitals in the
main energy level. i.e. in any given orbit. These five d orbitals are
conveniently represented as shown in the figures.
The five d orbitals, in an isolated, gaseous metal atom or ion, are
degenerate. If a spherically sym
symmetric
metric field of negative charges (i.e. ligand
ions or the negative end of the dipole) is placed around the metal, the
orbitals remain degenerate still. But all of them will be raised in energy as
compared to these ligands in a field free metal ion, the d orbitals remain
raised in their energies due to the repulsion between the negative field
(from the ligands) and the electrons in th
thee orbitals. The degeneracy of the d
orbitals will be removed. Now the d orbitals are split. The
consequences of this splitting are interpreted by the crystal field theory.
Two types of interactions are possible. overlap of orbitals, overlap of
orbitals; or d p bonding (back bonding) due to overlapping of the
full d orbitals on the metal with the empty p orbital on ligands. In most
transition metals complexes, the coordination is either 6 or 4. Therefore
such complexes are either octahe
octahedral
dral or tetrahedral in shape. The field
produced by the ligands is not spherically symmetrical. Therefore the d
orbitals are not all effected equally by the ligand field.

Under the influence of an octahedral ligand field the d orbitals split into
two groups
roups of different energies.
The extent to which the eg and t2g orbitals are separated in an octahedral
field is denoted by 0 or 10Dq. The average energy of the five d orbitals
is known as Baricentre of the d orbitals and it holds for all complexes,
regardless of geometry.

The d orbitals are split into two groups eg and t2g under the influence of an
applied external field from the ligands. The lobes of the eg orbitals (i.e.  

and   ) point along the three coordinate axes (,  and  axes). And the
lobes of the t2g orbitals (
; 
 and  orbitals) point in between the axes.

When six ligands approach the central metal atom or ion along the
coordinate axes i.e. , , ,
,
 and
 directions, the energy of the
 
 and   orbitals will increase much more than the increase in the
energy of 
, 
 and  orbitals. Thus under the influence of an
octahedral field of ligands, the d orbitals split into two groups. The
difference in energy between the two groups i.e. eg and t2g of orbitals is
given by 0 or 10Dq. This 0 is known as crystal field splitting energy.
Referring the energy of the Bari centre as zero, the eg orbitals are + 0.6 0
above the average level and the t2g orbitals are 0.4 0 below the average.
The magnitude of 0 can be estimated from the UV visible spectrum of
the complex formed. The magnitude of is influenced by three factors.
They are

a. The nature of the ligands

b. The charge on the metal ion
c. Whether the metal is in the first, second or third row of transition
elements
Spectrochemical series:

Ligands are labeled as weak and strong field ligands depending on the
degree of crystal field splitting caused by them. Ligands which cause only a
small degree of splitting are termed w
weak field ligands.

Ex:

And ligands which cause a large degree of splitting are called as strong
field ligands.

Ex: EDTA; NH3; H2N CH2 CH2 NH2; and

The common ligands can be arranged in the ascending order of their

crystal field splitting capacities i.e. their values. This series is called the
spectrochemical series. The series can be represented as shown below.

The spectrochemical series is an experimentally determined series. It is

difficult to explain the order and several other factors come into play. The
discussion
ion of these factors will be superfluo
superfluous
s at this level. So they are not
considered.

The electronic configuration of a central metal ion in a complex will follow

the Hunds maximum multiplicity rule. In a weak field of ligands, small
splitting of the energy levels occurs. Then it will be more favourable
energetically for electrons to occupy the upper eg level (in an octahedral
octahe
complex) rather than to pair up the electrons. In the case of a strong field
ligand field, large splitting of the energy levels occurs. In this case it takes
less energy to pair the electrons than to fill the electrons into the upper
energy level. Hence
ce the electrons get paired. Accordingly two different
configurations may be possible. The first one is known as high spin
complex and the later one is known as low spin complex.

Tetrahedral complexes:

A regular tetrahedron can be related to a cube. The p

positions
ositions of the central
metal and the ligands are shown in the figure for a tetrahedral complex.
The energy of the d orbitals, i.e. eg and t2g, is raised as the ligands
approach the central metal atom or ion. The energy of the t2g orbitals is
increased most
ost because they are closest to the ligands. The splitting of the
d orbitals is shown in the figure below.
The magnitude of the crystal field splitting (represented by t) in tetrahedral
complexes is considerably less than in the octahedral fields. The relation
between octahedral field splitting ((0) and the tetrahedral field splitting (
( t)
is given as

t = 0

Square planar
ar complexes:

Now the d orbital splitting be written in the same manner as we did for an
octahedral or a tetrahedral ligand ffield.

The four ligands in a square plan

planar arrangement gives the d orbital
splitting shown in the figure above. In this is raised above all others.
This arrangement becomes energetically favourable when the crystal field
fie
is strong.

Ex: [Ni(CN)4]-2

The sum of the three

hree distinct orbital splittings shown in the above figure
i.e. (1 + 2 + 3), is denoted by sp. The theory predicts sp = 1.3 0 for
complexes of the same metal and ligands w
with
ith the same metal to ligand
bond lengths.

d stabilization energy (LFSE):

Ligand field

The ligand field stabilization energy (LFSE) is a measure of the net energy
of occupation of the d orbitals relative to their mean energy.

To calculate the LFSE consider an octahedral complex. The splitting of the

orbitals is known. Let there be number of electrons in the t2g orbitals and
number of electrons in the eg orbitals. Then the electron distribution in the
octahedral field is written as .

In an environment, the energy of each t2g orbital is 0.40 and that of an eg

orbital is + 0.60. Then the net energy relative B
Bari centre for electron
configuration of an octahedral complex is the ligand field stabilization
energy. It is equal to {-[- 0.4
0.40( )] + 0.60( )]} = {-[+0.6 0.4 ]0} = [0.4
0.6 ]0

The LFSE is generally only a small fraction of the overall interaction

between the central metal atom and the ligands. This interaction increases
across a given period on account of the decrease in the ionic radius (M+2)
along the series.

Example 1:

The central metal ion has a d8 configuration. In an octahedral ligand field,

the splitting of the d orbitals in a strong field is known to us. The
T half head
arrows
rrows in the figure represent electrons. Since the ligand field
eld is strong, the
magnitude of 0 is large. Therefore electro
electrons
ns get paired up according to
Hunds
nds maximum multiplicity rule. On full occupation of the orbitals by the
electrons, we have = 6 and = 2. Then

LFSE = [0.4 0.6 ]0 = [(0.4)(6) (0.6)(2)]0

= 1.20

Example 2:

To calculate the LFSE for a tetrahedral ion of d6 configuration in a weak

ligand field. The splitting
ting of the orbitals is given by using the notation as
, the value of and are 3 and 3 respectively.

Therefore LFSE = {-[(0.4)3

[(0.4)3 ]+ (0.6)3t}

= 0.6t
Assignment questions:

For both octahedral and tetrahedral complexes practice writing the crystal
field splitting for different dx configurations

1. Explain an octahedral complex formation in terms of crystal field splitting

2. Write a short note on
a. The magnitude of and its influencing factors
b. Spectrochemical series
3. Write the crystal field splitting of d orbitals in
a. a tetrahedral ligand field (weak lligand)
b. a square planar
ar complex in a strong ligand field
4. What do you understand by ligand field stabilization energy? Explain
with a suitable example