CFT 1

Crystal field
theory
Crystal Field Theory
This Theory was developed by

The H.Bethe and Vleck in 1930.
It is based on the assumption that metal

Ion and Ligand act as point charges and
interaction between them purely electrostatic.
▪ The transition metal ion is surrounded by ligands with lone pair of electrons
▪ The interaction between metal ion and ligands are purely electrostatic. in
other words the bond between metal and ligand is considered 100% ionic
▪ The ligands surrounding the metal produce electric field this field influence
the energies of the d-orbital of Central metal ion
In a free metal ions all the five d-orbitals are degenerate
However, on the approach of ligands, the orbital electrons are repelled

by The Lone pair of Ligands. the repulsion raises the energy of d-
orbitals
▪ d-orbitals have different orientations therefore d-orbitals will experience
different interaction from the Ligand
The orbital lying in the direction of the Ligands will experience better
repulsion and their energies will be raised to a greater extent
The orbitals not lying along the approach of the ligands will face
smaller interaction that's why their energies will be raised to a lesser
extent
▪ The electric field of ligands splits up the energies of 5 d-orbitals
this conversion of 5 degenerate d-orbitals of metal ion into different
sets of orbitals having different energies in the presence of electric
field of ligands is called crystal field splitting
▪ The crystal field splitting will be different in different structure with
different coordination number
Comparison With VBT
❖ In contrast with VBT which is essentially a theory

for covalent bonding CFT is an ionic modal
❖ Metal-ligand bonds are described as resulting

from the attraction of positive metal ion for
negatively charged ligands
❖ In CFT covalent interaction are totally neglected
VBT Totally covalent character
CFT Express the ionic character

Crystal Field Theory
Calculations of coordinate bond energies can be made using classical

potential energy equations that take into account the attractive and
repulsive interactions between charged particles
q1 and q2 are charges on the interacting ions

r is the distance that separates ion centres
3d 4s
Ti +2 [Ar]
Ti +4 [Ar]
In a free Ti4+ ion, one isolated from all other species, the electronic configuration is
ls2 2s2 2p6 3s2 3p6; no d electrons are present. The five empty 3d orbitals of this ion
have identical energies. This means that an electron may be placed in any one of
these d orbitals with equal ease. Orbitals that have the same energy are called
degenerate orbitals.
[ TiF6 ] 2-
In [TiF6]2-, the Ti4+ ion is surrounded by six F– ions. These F– ions make it
much more difficult to place electrons in the Ti4+ d orbitals due to
repulsion of the electrons by the negative charge on F – ions. In other
words, the energy of the d orbitals increases as F– ions (or other ligands)
approach the orbitals .
If the six F– ions surrounding Ti4+ in [TiF6]2– were situated equally near
each of the five d orbitals of Ti4+ , all of these d orbitals would have the
same energy (they would be degenerate), but an energy considerably
greater than that which they had in the free Ti4+ ion. However, an
octahedral complex in which all d orbitals remain degenerate is but a
hypothetical situation.
❖ The complex [TiF6]2– has an octahedral

structure; for convenience, we shall visualize
this complex with the six F– ions residing on
the x, y, and z axes of a cartesian coordinate
system. In this orientation, F– ions are very
near the dx2–y2 and dz2 orbitals, which are
referred to as eg orbitals
▪ These eg orbitals point directly at the F– ligands,
▪ whereas the dxy, dxz, and dyz orbitals—called t2g orbitals—point
between the ligands.
Therefore, it is more difficult to place electrons in eg orbitals than in
t2g orbitals, which means that eg orbitals are of higher energy than
t2g orbitals.
This conversion of the five-degenerate d
orbitals of the free metal ion into groups
of d orbitals having different energies is
the primary feature of CFT; it is known as
CF splitting.
❑ In an octahedral arrangement of ligands, the
t2g and eg sets of d orbitals have different
energies. The energy separation between
them is given the symbol ∆o.
❑ It can be proved for an octahedral system that
the energy of t2g orbitals is 0.4 ∆o less than
that of the five hypothetical degenerate d
orbitals that result if crystal field splitting is
neglected . Therefore, the eg orbitals are 0.6
∆o higher in energy than the hypothetical
degenerate orbitals.
❑ The symbols eg and t2g are terms used in the
mathematical theory of groups. The t refers to
a triply degenerate set of orbitals; the e, a
doubly degenerate set.
concept of crystal field splitting difficult to visualize It may, however, be
helpful to develop a simple physical picture of crystal field splitting.
Imagine that the metal ion with its electron cloud can be represented by a
sponge ball. Now consider what happens when a rigid spherical shell
(corresponding to ligands) is forced around the outside of the ball. The
volume of the ball decreases, and the system has a higher energy, as is
evident from the fact that the sponge will expand spontaneously to its
original volume upon removal of the constricting shell.
This change in energy corresponds to the increase in energy that results from
repulsion between electrons in a metal ion and electrons of ligands in the
hypothetical complex.
• Now if the rigid shell is allowed instead to concentrate its total force on six
particular spots (for example, the corners of an octahedron), then the
sponge is pressed inward at these positions but bulges outward between
them.
• Compared with the spherically constricted system, the sponge at the six
points of high pressure is at a higher energy and at the bulges between is at
a lower energy. This corresponds to crystal field splitting with bulges
related to t2g orbitals and points of depression related to eg orbitals.
Octahedral complex with 1-d electron
In an octahedral complex that contains one d electron (for example,

[Ti(H2O)6]3+ that electron will reside in the d orbital of lowest energy.
In fact, the d electron goes into a t2g orbital that has an energy 0.4∆o
less than that of the hypothetical degenerate orbitals. Thus the
complex will be 0.4 ∆o more stable than the simple electrostatic
model predicts. In simple terms, we can say that the d electron, and
hence the whole complex, has a lower energy as a result of the
placement of the electron in a t2g d orbital that is as far from the
ligands as possible. The 0.4 ∆o is called the
crystal field stabilization energy (CFSE) for the complex.

CFT 1

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Crystal field

This Theory was developed by

It is based on the assumption that metal

In a free metal ions all the five d-orbitals are degenerate

However, on the approach of ligands, the orbital electrons are repelled

❖ In contrast with VBT which is essentially a theory

❖ Metal-ligand bonds are described as resulting

❖ In CFT covalent interaction are totally neglected

VBT Totally covalent character

CFT Express the ionic character

Calculations of coordinate bond energies can be made using classical

q1 and q2 are charges on the interacting ions

❖ The complex [TiF6]2– has an octahedral

In an octahedral complex that contains one d electron (for example,

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