COTTON UNIVERSITY

department of chemistry
student seminar
UG 5th semester
(core)2023

PRESENTED BY-
Trinalee Talukdar(CHM2132005)
Debaprotim Kalita (CHM2132032)
Tinku Talukdar(CHM213243)
Chanjyoti Kalita(CHM2132064)
CRYSTAL FIELD THEORY (CFT)
 CONTENTS
• Introduction
• What is CFT ?
• Assumptions of CFT
• Shape of d-orbital
• Non axial and axial orbital
• Energy of d orbital
• Splitting of d-orbitals in Octahedral Ligand Field
• Pairing energy
• CFSE
• Factors affecting CFSE value
• Jahn-Teller Effect
• Applications of CFT
• Limitations of CFT
 INTRODUCTION

There are mainly three theories which are used to

describe the nature of metal-ligand bonding in
coordination compounds.

1. Valence Bond Theory(VBT):VBT was proposed by Linus

Pauling and J. C. Slater in 1927.
2. Crystal Field Theory (CFT):CFT was proposed by Hans Bethe
in 1929.
3. Ligand Field Theory(LFT) or Molecular Orbital Theory(MOT) :
Developed by J.H.Van Vleck in 1935.
 Crystal Field Theory
 The model that largely replaced valence bond theory for
interpreting the chemistry of coordination compounds was
the crystal field theory , first proposed in 1929 by Hans
Bethe.
 This model was based on a purely interaction between the
ligands and the metal ion in the complexes with various
geometries like octahedral , tetrahedral, square planer etc.
 CFT is based on the concept that when the negative
charges of the incoming ligands ( or the negative ends of
dipolar molecules like NH3 and H2O)attract positively
charged metal ion , there is also repulsive interaction
between d electrons present on the metal ion and the
ligands.
 Certain assumptions are taken while dealing
with CFT-
1)CFT does not consider covalent bonding in
coordination complexes.
2)In CFT , the bonding between the metal and the
ligands arise from the electrostatic force of
attraction.
3)The interaction between the electrons of the metal
ion and the electron density of the ligand is
repulsive which causes splitting of the d- orbital of
the metal ions of the coordination compound.
4)CFT does not consider any orbital overlap between
the metal and the ligands.
 Shapes of d-orbital.

• In order to understand clearly the interactions that

are responsible for crystal or ligand field effect in
transition metal complexes.
• There are five wave functions that can be written
for orbitals having the typical four lobed form.
• The figures are given below-
Figure 1: shapes of d
orbitals.
dxy : lobes lie in
between the x and y axis.
dxz : lobes lie in
between the x and z axis.
dyz :lobes lie in
between the y and z axis.
dx2-dy2:lobes lie on the
x and y axis.
dz2 :there are two
lobes on the z axis and
there is a donut shape
ring that lies on the xy
plane around the other
two lobes.
Non axial orbitals and axial orbitals.
 Energy of d orbitals
• In an octahedral complex, when the ligands approach towards
the metal ion these d orbital of metal ion are repelled by ‘-ve’
point charge on the ligands . The repulsion raise the energy of
all the 5 orbitals equally.
• Since the lobes of the two eg orbitals lie directly along the
path of the approaching ligands, these two orbital experience
greater repulsion in comparison to the t2g orbitals as the lobe
of these orbitals are in between the approaching ligand.
• Therefore, the energy of eg set of orbitals is increase and t2g
set of orbitals decrease.
Diagrammatical representation
Splitting of d-orbitals in
Octahedral Ligand Field
 In octahedral complexes, the ligands approach along the axes
 The electrostatic repulsion between the ligands and the electrons of the
central metal atom or ion will be much greater when the electrons are
housed in eg set of orbitals (dx2-y2 and dz2 orbitals) which are directly points
towards the ligands.
 Electrons are housed in the t2g set of orbitals (dxy, dxz, dyz orbitals)
experienced comparatively less repulsive interaction as they are directed in
between the Cartesian coordinate axes.
 The energy difference between the eg and t2g set of orbitals is measured in
terms of crystal field splitting parameter,Δo or 10 Dq.
• For strong ligand field: crystal field splitting high; Δ(oct) > Pairing Energy (P); results
low spin metal complexes

• For weak ligand field: crystal field splitting low; Δ(oct) < Pairing Energy (P); results
high spin metal complexes
High spin and low spin situations for a d6 metal
Pairing Energy

 The energy required to

force two Unpaired
electrons in an orbital is
known as pairing Energy
 High Spin Complexes
Doesn’t show pairing
energy.
 CRYSTAL FIELD STABILIZATION ENERGY (CFSE)

 The energy difference between the distribution of electrons

in a particular crystal field and that for all electrons in the
hypothetical spherical or uniform field levels is called the
crystal field stabilization energy (CFSE)
 As we have seen, the energy difference between t2g and eg
orbitals is defined as Δo. The energy level of each of the two
eg orbitals would be 0.6 Δo above the zero of energy
(barycenter) , whereas the energy level of each of the three
t2g orbitals would be 0.4 Δo below the zero energy.
 Calculation of CFSE

 [Fe(H20)6]3  [Fe(CN)6]3-
+
 Strong field
 Weak field
 High spin  Low spin

CFSE = 3 ×( -0.4 ∆o) + 2×(+0.6∆o)

CFSE = 5× (-0.4∆o) + 0
= -1.2 ∆o + 1.2 ∆o
= -2.0 ∆o
=0
Consider the example, the [Ti (H2O)6] 3+ ion . Ti 3+ has a d1 electron configuration
with the electron occupying t2g, the crystal field stabilization energy (CFSE) is -0.4
Δo . For d2, the CFSE = -0.8 Δo and for d3, CFSE = -1.2 Δo. Upon reaching the d3
configuration, however, the t2g level becomes half-filled and there are no further
orbitals of this energy to accept electrons without pairing.

Distribution of
electrons and
CFSE for d1-d3
configurations
Factors Affecting the Magnitude of
CFSE Δ
1- Oxidation state of the metal ion : The magnitude of Δ
increases with increasing ionic charge on the central metal ion. The
cations from atoms of the same transition series and having the same
oxidation state have almost the same value of Δ but the cation with a
higher oxidation state has a larger value of Δ than that with lower
oxidation state
Δo for [Fe(H2O)6]2+ = 10,400 cm-1 ………3d6
Δo for [Fe(H2O)6]3+ = 13,700 cm-1 ………3d5
Δo for [Co(H2O)6]2+ = 9,300 cm-1 ……….3d7
Δo for [Co(H2O)6]3+ = 18,200 cm-1 ………3d6
This effect is probably due to the fact that the central ion with higher
oxidation state (higher charge) will polarize the ligands more effectively
and thus the ligands would approach such a cation more closely than
they can do the cation of lower oxidation state, resulting in larger
splitting.
2- Nature of the metal ion : Significant differences in Δ also occur for
analogous complexes within a given group,
the trend being 3d < 4d < 5d.
In progressing from Cr to Mo or Co to Rh, the value of Δ increases by as
much as 50%. Likewise, the values for Ir complexes are some 25% greater
than for Rh complexes.

Δo for [Co(NH3)6]3+ = 23,000 cm-1…….3d6

Δo for [Rh(NH3)6]3+ = 34,000 cm-1 ……4d6
Δo for [Ir(NH3)6]3+ = 41,000 cm-1 ……5d6

An important result of this trend is that complexes of the second and third
transition series have a much greater tendency to be low spin than do
complexes of the first transition series.
Geometry of the complex : The splitting in an octahedral field is about
twice as strong as for a tetrahedral field for the same metal ion and the
same ligands . In tetrahedral complex the ligands are directed much less
efficiently than in octahedral complex

This relationship is observed for VCl4 and [VCl6] 2- , as well as for

[Co(NH3)4] 2+ and [Co(NH3)6] 2+ .
4- Nature of the ligands : The magnitude of Δ varies from
strong to weak ligands. Strong ligands are those which exert a
strong field on the central metal ion and hence have higher
splitting power consequently relatively lower splitting power. Thus
strong ligands (e.g. CN- ) give larger value of Δ and weak ligands
(e.g. F- ) yield a smaller value of Δ . Based on similar data of the
absorption spectra for a wide variety of complexes, it is possible to
list ligands in order of increasing field strength in a
spectrochemical series.
Based on similar data of the absorption spectra for a wide variety of
complexes, it is possible to list ligands in order of increasing field strength
in a spectrochemical series. The common ligands can be arranged in the
order of their increasing splitting power to cause d-splitting. This series
called spectrochemical series.

This series shows that the value of Δ in the series also increases from
left to right. The order of field strength of the common ligands shown
above is independent of the nature of the central metal ion and the
geometry of the complex.
 JAHN-TELLER THEORM or
JAHN-TELLER EFFECT :
In 1937, Jahn and Teller put forward a remarkable theorem to explain why
some 6-coordinated complexes (octahedral complexes) undergo distortion
and distorted octahedral geometry.
Theorem: In a nonlinear molecule, if degenerate orbitals are
asymmetrically occupied, a distortion will occur to remove the degeneracy
by lowering the symmetry and thus by lowering the energy.

❖ Octahedral complexes that are susceptible to Jahn-Teller distortions have

degeneracy either in t2g or eg set of orbitals. The effect is most pronounced
when degeneracy occurs in the eg than the t2g set of orbitals, because eg
orbitals are pointing directly at the ligands. Hence, complexes with eg1 or
eg3 configurations (high spin d4 , low spin d7 and d9 ) will show significant
distortions.
❖ The theorem predicts which configurations will show distortions.

Types of Jahn-Teller Distortions

❖ Axial Elongation (z-out distortion): Occurs when the degeneracy is

broken by the stabilization (lowering in energy) of the d orbitals with a z-
component, while the orbitals without a z-component are destabilized
(higher in energy).
❖ Axial Compression (z-in distortion): Occurs when the degeneracy is
broken by the stabilization (lowering in energy) of the d orbitals without
a z-component, while the orbitals with a z-component are destabilized
(higher in energy).

❖ The theorem can not predict the type of distortion occurs (z-out vs.
z-in). However, because axial elongation weakens two bonds but
equatorial elongation weakens four, axial elongation (z-out) is more
common than axial compression (z-in).
 Applications of Crystal Field Theory: Lattice Energy

M 2 of first row transition metals

F

The lattice energy is expected to increase continuously across the transition

series as the ionic radii of the metals decrease (lattice energy is proportional
to 1/(r+ + r_ ). Deviations from expected line can be attributed to CFSE.
 Ca2+ ,Mn2+ ,and Zn 2+ have d0 ,d5 and d 10 ,thus CFSE is 0. They follow
the expected line .Other metal ions deviate from the expected line due to
extra CFSE. CFSE increases from d1 to d3 , decreases again to d5, then rises
to d8.
 Applications of Crystal Field Theory : Ionic Radii

○ high spin
● low spin

?
?
●
●
Ionic radii of M2+in MCl2

For a given oxidation state, the ionic radius is expected to decrease continuously
across a transition series. Deviations from the expected line can be attributed to
different electronic configurations (resulting from crystal field splitting).
For weak field case, ionic radius starts to increase with t2g 3eg 1 configuration as the
electron in the eg level experience repulsion with the ligands. For strong field case,
ionic radius starts to increase with t2g 6eg 1 configuration.
 Applications of Crystal Field Theory : Enthalpy of
Hydration/Formation

M2+(g) + 6H2O(l) = [M(H2O)6]2+(aq)

❖ Stronger electrostatic attraction energy between ions and water dipoles increases
hydration enthalpy (ΔH). ΔH is proportional to the charge but inversely proportional to
the radius of the ion. ΔH should increase (become more negative) continuously across
transition series due to decrease in ionic radii. But, experimental ΔH values show
characteristic double-humped shape.
The Color of Coordination Compound
A substance exhibits color because it has the
property to absorb certain radiations from the
visible region of spectrum.
The wavelength of the visible spectrum is in
the range of 400 to 700 nm.
Condition of absorption
The energy gap between the eg
and t2g orbitals, ,(the
crystal field splitting ) equals
the energy of a photon :

As , varies , will also

vary
and the color of the compound
will change.
Absorption of a photon
causes a jump from a t2g
to an eg orbital
Transition metal ions
have color due to the
absorption of specific
Wavelengths of light .
This absorption is
caused by the
movement of electrons
within the metal ion ,
Which is unique for
each metal ion. As a
result of the absorption
of some selected wave
lengths of visible lights,
the complexes appear
coloured .
 The color of the complexes depends on the following factors:
1. Configuration should be between d1 to d9
a)[Zn(NH3)4]
b)[Cu(NH3)4]+1
c)[Cd(NH3)4]+2
Ques: Why all the complex colourless or white ?
Ans :Since Zn,Cu+1,Cd+2 all are in 3d10 electronic configuration and
there are no unpaired electrons available for excitation, the
complexes does not absorb any visible light.
2.Ligand should be present for splitting

[Ti(H2O)6]+3 heat Ti + 6H2O

(violet) (colourless)
 Limitations of CFT
1.CFT considers the splitting of d- orbital but it does not consider the
splitting of other orbitals in the ligand field environment.

2.CFT considers the splitting of d- orbital but it does not consider

the splitting of other orbitals in the ligand field environment.

3. According to the CFT metal ligand bond having 100% ionic

character but from the various experiment it was froved that metal
ligand bonds having certain extent of covalence with the ionic
character.e
BIBLIOGRAPHY
 Inorganic chemistry, James E. Huheey

 Principles of Inorganic Chemistry, puri .

Sharma . Kalia