What is Crystal Field Theory?

The crystal field theory (CFT) was proposed by H. Bethe and V. Bleck. This theory
explains the bonding, properties, electronic spectra, and magnetism of metal
complexes more clearly.

The conversion of five degenerate d-orbitals of the metal ion into different sets of
orbitals having different energies in the presence of a crystal field of ligands is
called crystal field splitting. Crystal field splitting forms the basis of crystal field
theory.

Postulates of Crystal Field Theory

The postulates of CFT Theory is mentioned below:

1. The crystal field theory considers that the metal ion is situated in an electric
field caused by the surrounding ligands.
2. The attraction between the central metal and the ligand in a complex is
purely electrostatic. The negative end of the dipole of the neutral molecule
ligand is directed towards the metal ion.
3. The transition metal or ion is considered as a positive ion of charge equal to
the oxidation state.
4. The transition metal atom or ion is surrounded by a definite number of
ligands, it may be negative ion or neutral molecules having lone pairs of
electrons.
5. The ligands are considered as point charges and produce an electric field.
This electric field changes the energy of the orbitals on the metal atom or
ions.
6. Due to the repulsive force between the central metal ion and ligand, the
electrons on the metal ion occupy the dd-orbitals as far as possible from the
direction of approach of the ligand.
7. There is no interaction between the metal orbital and ligand orbitals.
8. In an isolated metal atom or ion, all the orbitals have the same energy, i.e., all
five d orbitals (dxy,dxz,dyz,dx2–y2anddz2)(dxy,dxz,dyz,dx2–y2anddz2) are
degenerate.

9. If the central metal atom or ion is surrounded by the spherical symmetric al field
of negative charges, the dd-orbitals remain degenerate. However, the energy of the
orbitals is raised due to the repulsion between the field and the electron on the
metal atom or ion.
10. In most transition metal complexes, the dd-orbitals are affected differently, and
their degeneracy gets lost due to the field produced by the unsymmetrical ligand.

Spectrochemical Series
The crystal field splitting depends upon the nature of the ligand. The ligands which
cause only a small crystal field splitting are called weak field ligands. The ligands
which cause a large crystal field splitting are called strong field ligands.

The arrangement of common ligands in the ascending order of crystal field

splitting (Δ)(Δ) is called spectrochemical series. The spectrochemical series in the
increasing order of crystal field splitting is:
I–<Br–<S2–<Cl–<NO–3<F–<OH–<EtOH–<C2O2–
4<H 2O<<EDTA<NH 3 <Py<Ethylenediamine<dipyridyl<0–phenanthroline<NO–2<CN–
<CO

Crystal Field Theory for Octahedral Complexes

In the octahedral complex ion, the ligand is represented by small negative charges
and the metal ion by positive change.

In octahedral complexes, as the ligands approach metal ions, there is repulsion

between the ligands and the dd-orbitals, thereby raising their energy relative to
that of the free ion. In five dd-orbitals, dx2–y2dx2–y2 and dz2dz2 orbitals have greater
repulsion with the ligands as compared to remaining three dd-orbitals,
i.e., dxy,dxzdxy,dxz and dyz.dyz.
Therefore, the energies of dxy ,dxz and dyz are lower than those of dx2–y2dx2–
y2 and dz2dz2 orbitals.
The dxy,dxz and dyz orbitals of lower energy are called t2gt2g orbitals and dx2–
y 2 ,d z2dx2–y2,dz2 orbitals of higher energy are called eg orbitals.
The difference of energy between the two sets of d- orbitals is called crystal field
splitting energy or crystal field stabilisation energy (CFSE). It is represented as ΔOΔ,
where ‘O’ stands for the octahedral complex.
The eg orbitals have +0.6Δ0+0.6Δ0 or 35Δ035Δ0 above the average energy level
and t2gt2g orbitals are –0.4Δ0–0.4Δ0 or –25Δ0–25Δ0 below the average.

In octahedral complexes, strong field ligands have high Δ0Δ0 value and they are low
spin complexes. Example: [Fe(CN)6]4–[Fe(CN)6]4– and [Co(NH3)6]3+[Co(NH3)6]3+
The weak field ligands have low Δ0Δ0 value and they are high spin complexes.
Example: [Fe(H2O)6]2+[Fe(H2O)6]2+ and [CoF6]3–[CoF6]3–
Crystal Field Theory for Tetrahedral Complexes
The splitting pattern of tetrahedral complexes is the reverse of the splitting pattern
of octahedral complexes. In tetrahedral complexes, dx2–y2dx2–y2 and dz2dz2 orbitals
have lower energy than dxy,dxzdxy,dxz and dyzdyz orbitals.
The difference of energy between two energy levels is Δt(Δt=49Δ0)Δt(Δt=49Δ0). Due
to this small energy gap, electrons do not pair. Therefore, tetrahedral complexes
have a high spin configuration.

1.Crystal Field Theory for Octahedral Complexes

a. Electrons in d-Orbitals

All d-orbitals have the same energy (in spite of their different shapes and/or
orientations) on a bare metal ion. However, some d-orbitals have different energies
from the others in a metal complex. This is called d-orbital splitting.

Consider the 5 d-orbitals in an xyz coordinate system. We will not try to give
perspective drawings, rather we will rotate the coordinate system so that it is easy
to draw the orbitals.

The odd-shaped dz2 orbital results because there are six solutions to the
Schroedinger equation for the angular momentum quantum number l (the d-
orbitals), but only 5 solutions are independent. The combination of two orbitals
produces the unique dz2 orbital:
b. Splitting of the d-Orbitals in an Octahedral Field

Let's look at what happens to the energies of electrons in the d-orbitals as six
ligands approach the bare metal ion:

If we compare the dxy and the dx2-y2, we can see that there is a significant difference
in the repulsion energy as ligand lone pairs approach d-orbitals containing
electrons.

Electrons in the dxy orbital are concentrated in the Electrons in the dx2-y2 orbital point
space between the incoming ligands. straight at the incoming ligands.

Now, dxz and dyz behave the same as dxy in an octahedral field, and dz2 behaves the
same as dx2-y2. This means that the d-orbitals divide into two groups, one lower
energy than the other, as shown in the following diagram.
The dxy, dxz, and dyz orbitals are collectively called the t2g orbitals, whereas the
dz2 and dx2-y2 orbitals are called the eg orbitals. The octahedral splitting energy is
the energy difference between the t2g and eg orbitals. In an octahedral field, the
t2g orbitals are stabilized by 2/5 Deltao, and the eg orbitals are destabilized by 3/5
Deltao.

c. Consequences of d-Orbital Splitting: Magnetism

Let's consider the complexes [Fe(H2O)6]Cl3 (mu = 5.9 B.M.; 5 unpaired electrons)
and K3[Fe(CN)6] (mu = 1.7 B.M.; 1 unpaired electron).

The free Fe3+ ion is a d5 ion. The two complexes are 6-coordinate and octahedral.
First let's look at the d-orbital diagram for [Fe(H2O)6]3+:

The first three electrons go into t2g orbitals unpaired. The 4th and 5th
electrons must choose whether to pair up with electrons already in
t2g (which costs energy) or to go into higher energy eg orbitals (which
also costs energy). In this case, the splitting energy is less than the
pairing energy so the 4th and 5th electrons go into the eg orbitals.
d-orbital diagram
for [Fe(H2O)6]3+

Now let's consider the [Fe(CN)6]3- ion. Again we have five d-electrons. However,
there is only one unpaired electron, so the 4th and 5th electrons must pair with
electrons already in t2g orbitals. this happens because the octahedral splitting
energy is much greater in the hexacyanoferrate(III) ion than it is in the
hexaaquoiron(III) ion. That is, the cyanide ligand causes a much greater d-orbital
splitting than water does.

The first three electrons go into t2g orbitals as before. Now, however,
the splitting energy is much greater so it is less energetically costly for
electrons to pair up in the t2g orbitals than to go into the eg orbitals.

d-orbital diagram for

[Fe(CN)6]3-

[Fe(CN)6]3- is called a low-spin complex because it has the lowest number of

unpaired spins (electrons) possible for an octahedral iron(III) complex.
[Fe(H2O)6]3+ is called a high-spin complex because it has the highest number of
unpaired spins for an octahedral iron(III) complex. The terms "high-spin" and
"low-spin" do not refer to specific numbers of unpaired electrons, but rather to
different electron configurations in d-orbital diagrams that result from the pairing
energy being greater than or less than the splitting energy.

d. Consequences of d-Orbital Splitting: Colour

Colour in transition metal complexes is due to an electron being excited from one
d-orbital to a higher-energy d-orbital. In the case of octahedral complexes, an
electron is moves from a t2g orbital to an eg orbital. The energy difference for the
first transition series generally falls in the visible region. Absorption of one colour
in the visible spectrum results in the ion having the complementary colour.

The amount of d-orbital splitting depends on the ligands. thus different ligands
have different splitting energies, and different colours result.

Excitation of an electron from a t2g orbital to an eg orbital causes the red colour of
[Ti(H2O)6]3+ ions. (Ti3+ is a d1 ion).

2. Tetrahedral Complexes

a. d-Orbital Splitting in Tetrahedral Coordination. A cube, an octahedron, and

a tetrahedron are related geometrically. Octahedral coordination results when
ligands are placed in the centers of cube faces. Tetrahedral coordination results
when ligands are placed on alternate corners of a cube.

Octahedral complex in a cube. Ligands are Tetrahedral complex in a cube. Ligands are on
on the centers of the cube faces. alternate corners of the cube.
Now consider the effect of the ligands on the energies of the d-orbitals in
tetrahedral coordination, with the dyz and dz2 orbitals as examples. An electron in
the dyz orbital can approach the ligand to within a distance of a/2, where a is the
cube edge length. However, an electron in dz2 only approaches the ligands at a
distance of a/2(20.5), a distance 1.414 times as long as the distance in the dyz case.
This means that the dz2 orbital is lower in energy than the dyz orbital, exactly the
opposite case as in octahedral coordination.

The dyz orbital in tetrahedral coordination. The dz2 orbital in tetrahedral coordination:
Electrons in this orbital can approach within a electrons in dz2 are further from the ligands
distance of a/2 to ligand electrons. than electrons in dyz.

The dxz and dxy orbitals behave the same way as dyz, and dx2-y2 behaves the same
way as dz2. The resulting d-orbital splitting diagram for tetrahedral coordination is
the inverse of the diagram for octahedral coordination, as shown below.

The dxy, dxz, and dyz orbitals are the t2 orbitals, and
they are higher in energy than the e orbitals (dz2 and
dx2-y2) in tetrahedral coordination.
The energy difference between the
t2 and the e orbitals is called the
tetrahedral splitting energy.
(Note that the orbitals are labelled t2 and e, not t2g and eg; g refers to a geometry,
such as octahedral, that has a center of symmetry. The tetrahedral geometry has no
center of symmetry).

b. Crystal Field Stabilization Energy in Tetrahedral Complexes. The

tetrahedral crystal field stabilization energy is calculated the same way as the
octahedral crystal field stabilization energy. The magnitude of the tetrahedral
splitting energy is only 4/9 of the octahedral splitting energy, or

As a result of the relatively small size of the tetrahedral splitting energy, there are
no low-spin tetrahedral complexes. It is always more energetically favorable to put
an electron into a t2 orbital rather than pair it in an e orbital.
Let's calculate the crystal field stabilization energy for a tetrahedral cobalt(II)
complex. Cobalt(II) is a d7 ion. The electronic configurations of the free ion and
the tetrahedral complex are shown below.

A table showing the crystal field stabilization energies for tetrahedral complexes
with different numbers of d-electrons is given below.

Crystal Field Stabilization Energies for Tetrahedral Complexes of d1 - d10 Ions

# of d-electrons Tetrahedral CFSE # of d-electrons Tetrahedral CFSE

1 -0.6 Deltat
2 -1.2 Deltat
3 -0.8 Deltat
4 -0.4 Deltat
5 zero
6 -0.6 Deltat
7 -1.2 Deltat
8 -0.8 Deltat
9 -0.4 Deltat
10 zero

3. Square Planar Complexes

a. d-Orbital Splitting in Square Planar Coordination. Square planar

coordination can be imagined to result when two ligands on the z-axis of an
octahedron are removed from the complex, leaving only the ligands in the x-y
plane. As the z-ligands move away, the ligands in the square plane move a little
closer to the metal.

The orbital splitting diagram for square planar coordination can thus be derived
from the octahedral diagram. As ligands move away along the z-axis, d-orbitals
with a z-component will fall in energy. The dz2 orbital falls the most, as its
electrons are concentrated in lobes along the z-axis. The dxz and dyz orbitals also
drop in energy, but not as much. Conversely, the dx2-y2 and the dxy orbitals increase
in energy. The splitting diagram for square planar complexes is more complex than
for octahedral and tetrahedral complexes, and is shown below with the relative
energies of each orbital.

b. Crystal Field Stabilization Energy in Square Planar Complexes. Square

planar coordination is rare except for d8 metal ions. Among the d8 metal ions
exhibiting square planar coordination are nickel(II), palladium(II), platinum(II),
rhodium(I), iridium(I), copper(III), silver(III), and gold(III). Copper(II) and
silver(II), both d9 ions, are occasionally found in square planar coordination.

All known square planar complexes of d8 ions are diamagnetic, because the
highest-energy orbital (dx2-y2) is greatly destabilized, and pairing in the dxy orbital
is more favorable than placing an unpaired electron in the dx2-y2 orbital.

The crystal field stabilization energy for a diamagnetic square planar d8 metal
complex is readily calculated by the usual method:
The pairing energy correction is included because a free d8 ion has 2 unpaired
electrons, but a square planar d8 complex has no unpaired electrons.

Crystal Field Stabilisation Energy

The difference of energy between the two sets of dd-orbitals is called crystal field
splitting energy or crystal field stabilisation energy (CFSE). It is represented as ΔΔ.
Crystal Field Stabilization Energy Table
Crystal field stabilisation energy (CFSE) of octahedral complex is as follow:

Factors Affecting the Magnitude of Orbital

Splitting Energy (Δ)(Δ)
1. Higher the oxidation state of the central ion, the larger the value of orbital
splitting energy.
2. In d-block (transition) elements, ΔΔ value increases
from 3d3d to 4d4d to 5d5d elements. Therefore, the elements of the second
series 4d4d and third series 5d5d have a greater tendency to form low spin
complexes than the first (3d)(3d) transition series.
3. The ΔΔ value of the coordination entity helps in the determination of the type
of complex. The ΔΔ value of the tetrahedral complex is nearly 50%50% of the
octahedral complex.
For the same metal ion, different ligands have different splitting amounts.

What are the Limitations of Crystal Field Theory?

The crystal field theory could explain the formation, structure, optical, and magnetic
properties of the coordination compound quite satisfactorily. But the crystal field
theory could not explain the following factors.

1. The existence of covalent bonding in some transition metal complexes.

2. The order of ligands in the spectrochemical series. As ligands are considered
as point charges, the anionic ligands should exert a greater splitting effect.
However, the anionic ligands are placed at the lower end of the
spectrochemical series.