Subject Chemistry

Paper No and Title Chemistry of d- block elements, Quantum Chemistry and

Spectroscopy
Module No and Title 07,

Introduction of Crystal Field Theory

Module Tag Video 07

Content Writer Course coordinator

Dr. Niraj Upadhyay Dr. Niraj Upadhyay

Assistant Professor Assistant Professor

Department of Chemistry Department of Chemistry
Dr. H. S. Gour Central University Dr. H. S. Gour Central University
Sagar, MP 470003, India. Sagar, MP 470003, India.
Reviewer
Content Co-writer
Dr. BhavanaSethi Dr. Hiendra Singh
Associate Professor & Head
Assistant Professor (Ex.), Department of Chemistry
Applied Science and Humanities Department, Pt. L.M.S.G PG College, Rishikesh,
Academy of Business and Engineering SDS University, Uttarakhand.
Sciences, Ghaziabad (U.P.)
Introduction

In the last module, we have discussed about the valence bond theory approach for explaining
bonding in coordination compounds. There you got to know that central metal provides vacant
orbitals equal in number to the available filled or sigma orbitals provided by the ligand. All these
vacant orbitals hybridized to produce equal number of equal energy orbitals and then overlap
with available sigma orbitals of the ligand. Since, there were possibilities of participation of
inner as well as outer d orbitals in hybridization, therefore the model suggested to chalk out the
participation of inner or outer d-orbital by finding value of experimental magnetic moment and
comparing with theoretical value of the spin only magnetic moment. Though, the theory is easy
to grasp and apply but is having serious limitations like, theory is lacking in understanding the
properties of coordination compounds, for example color, magnetic properties etc. Sometimes, it
is even difficult in finding the participation of inner orbital or outer orbital in hybridization, if
value of magnetic moment fails to explain that. Also, the model didn’t contain any quantitative
aspect and unable to explain the stability of coordination compounds.

It is therefore, valence bond theory was thought to have limited applicability and a new and
better theory was needed. During the period crystal field theory emerged with larger applicability
and more acceptability. Here in this module, we will learn about assumptions and detailed
explanation of crystal field theory.

Crystal Field Theory

The Crystal field model has largely replaced valence bond theory for interpreting the chemistry
of coordination compounds. It was first proposed in 1929 by Hans Bethe. Further modifications
were proposed by J. H. Van Vleck in 1935. It was a model based on a purely electrostatic
interaction between the ligands and the metal ion i.e. the coordination compounds were thought
in the direction of an ionic crystal lattice, where the major force of interaction is electrostatic
force. When a metal ion is surrounded by anions in a crystal, there is an electrostatic field
produced by the anions that alters the energies of the d orbitals of the metal ion. The field
generated in this way is known as a crystal field. Hence the name Crystal field theory. The
theory concentrates on the resulting splitting of the d orbitals into groups with different energies,
and uses that splitting to rationalize and correlate the optical spectra, thermodynamic stability,
and magnetic properties of complexes.
Assumptions of CFT:

1. The central metal cation of a complex is surrounded by ligands

2. The ionic ligands (e.g., F-, Cl-, CN- etc.) are regarded as negative point charges while the
neutral ligands (e.g., H2O, NH3, etc.) are regarded as negative point dipoles, where the negative
end of this ligand dipole is oriented towards the metal cation.
3. A positively charged central metal was considered as positive point charge, while a
neutral central metal atom was assumed as point positive dipole.
4. According to CFT, there is purely electrostatic or Coulombic attraction between
positively-charged metal ion and negatively-charged ligands.
5. CFT does not consider mixing of orbitals of metal ion and the ligands i.e., it does not
consider any orbital overlap.
6. When ligand approaches near to central metal ion in a spherical way, all the five filled d-
orbitals face equal repulsion. But to minimize energy of the formed molecule ligands arrange
themselves in different shapes that effect differently to different d- orbitals and therefore d-
orbitals split up.

Let’s explain the theory by taking an example of octahedral geometry. You all know octahedral
geometry forms for coordination number 6. That is in the specific example, metal M is
surrounded by six ligands L. So, our generalized example is of [ML6], which may or may not be
a neutral species (Figure 7.1).

Crystal Field Splitting in an Octahedral Field:

So, according to the theory, metal M is a positive point charge or positive point dipole, while
ligands are negative point charges or negative point dipoles. The attraction between the two is
completely electrostatic in nature. Therefore, initially let us consider that the ligands are situated
at the infinite distance from the ligand. According to basic assumptions lines of forces originate
from cations and falls on to anion. The electrostatic force of attraction is completely responsible
for the formation of chemical bond and the bond energy can be determined by the formula:
Bond Energy = q1q2/4πϵr2

I think you all are familiar with this equation. Here q1 and q2 represents charges of cation i.e.
central metal and anion i.e. ligand respectively and r is the bond distance between the metal and
the ligand. Though, the value obtained for the bond energy by this way doesn’t match with the
experimental value of the bond energy, specifically in the case, where M is a transition metal
atom or ion. The difference between main group and transition meal is by d- orbitals only. So,
let’s elaborate the electrostatic effect on d- orbitals of central metal ions.

So, when ligand was situated at the infinite distance from the metal, it get attracted and due to
that attraction energy of the five metal d- orbitals start decreasing. Till a certain distance from
metal attraction dominates. But, at a certain point electrons present in metallic orbitals feels
repulsion with the incoming negatively charged ligands. That increases energy of five d-orbitals.
This equal increase of energy is however a hypothetical situation (Figure 7.2).Now, to minimize
the energy of central metal ion, ligands orient themselves in a specific arrangement. In case of
ML6 the arrangement is octahedral.

⮚ Understanding the octahedral geometry:

It’s better to understand a three dimensional model in terms of cubical room (Figure 7.1). The
metal stays at the center of the cube and considered as origin of the three dimensional
coordinates. The three axes X-, Y- and Z- are pointing towards the corners of regular octahedron.
In a cube, you can imagine the three perpendicular lines passing through the central metal ion as
the three axes X-, Y- and Z-. All the six ligands are approaching from the directions of these axes
only and occupy the positions of each of the face center of the cube. So, metal is at the body
center of the cube and ligands occupy the position of all the face center of the cube. It is
therefore, two ligands are approaching towards M on each of the axis but from the opposite
direction.
 Figure 7.1: Octahedral geometry of an octahedral complex

You can see this in a model shown here. As you can see all the six ligands in the octahedral
geometry are interacting through axial positions. When ligand approaches a certain distance from
the metal, the metal orbitals that occupy electrons start getting significant repulsion from the
incoming ligands. The orbital s-- is spherical and p orients in px, pyandpz axis and therefore the
energy of all these orbitals increases equally. But, the same is not the case with the d-
d orbitals. d-
subshell is formed by thee combination of five dd-orbitals i.e. dxy, dyz, dzx, dz2 and dx2-y2 orbitals.
The shape of five d-orbitals
orbitals are presented here in the Figure 7.2.

⮚ Splitting of d–orbitals
orbitals in an Octahedral Field

Figure 7.2: Orientation of the five d

d-orbitals w.r.t the ligands in an octahedral complex.
(a) eg orbitals and (b) t2g orbitals

Theelectron lobes in dz2 and dx2--y2 orbitals are along the axes and are concentrated close to the
ligands, whereas electron lobes in d xy, dyz and dzx orbitals are concentrated in regions that lie in
between the ligands.As a result, dz2 and dx2-y2 set of d orbitals are repelled more strongly by the
negative charge on the ligands and therefore energy of these orbitals increases with respect to
spherically symmetrical arrangement. While, the set of orbitals d xy, dyz and dzx which lie in
between the axes, get less repulsion in terms of spherical arrangement of d-subshell. It is
therefore, in octahedral geometry, the energy of five d-orbitals are no more identical and
therefore splits up in these two sets of orbitals. A set of two orbitals is represented in group
theory by letter e and set of three orbitals are represented by letter t. The molecules which are
symmetric with respect to center of symmetry, if it is having symmetric orbitals with respect to
center of symmetry, then the subscript g is given that stand for gerade in the symmetric
representation. But if orbital of such symmetrical orbitals doesn’t contain any center of
symmetry then subscripts u that stands for ungerade have to be introduced. The origin of
subscript 1 and 2 you try to find. An octahedral molecule contain center of symmetry. As,
distance traveled in one direction for getting a ligand is equal when we go in the opposite
direction to reach another ligand. So, it is desirable to find symmetry of d-orbitals in terms center
of symmetry. You can see all the d-orbitals are symmetrical with respect to center of symmetry.
Because when we go in a particular direction, the phase of the lobe of the d-orbital remains same
as and when we go in the opposite direction of this. So, for showing all the d- orbitals a subscript
g have to be introduced. You can see here in the diagram. So, the set of two orbitals here d z2 and
dx2-y2, which contain center of symmetry can be represented by the representation e g and the set
of three orbitals which is repelled less by incoming ligand i.e. d xy, dyz and dzx is represented by t2g
orbitals. Thus under the influence of approaching ligands, the five d-orbitals which were
originally degenerate in the free metallic cation are now split into two levels viz. t 2g level which
is triply degenerate and is of lower energy and eg level which is doubly degenerate and is of
higher energy. The separation of five d-orbitals of the metal cation into two sets having different
energies is called Crystal Field Splitting.
The energy gap between t2g and eg set of orbitals is represented by ΔO or 10 Dq where the
subscript O in ΔO signifies an octahedral crystal field. This energy difference which arises
because of the differential electrostatic field applied by the ligands on the d-orbitals of the central
metal cation is called as Crystal Field Splitting Energy. The energy level that corresponds to the
hypothetical spherically symmetrical environment defines the bary center of the array of levels.
The two eg orbitals lying at 3/5 Δo above the bary center and the three t2g orbitals lying at 2/5 Δo
below it (Figure 7.3). These value can easily be determined by following two equations:
Let, x represents energy of each of the t2g orbitals and y represent energy of each of eg orbitals.
Let bary center is our reference point and therefore x will have some negative value and y is a
positive quantity. Since, the gap of energy between t 2g and eg is represented by Δo. Thus, the
energy difference between eg and t2g level is equal to Δo.
Therefore, Y - X = Δo …….. (1)
Also, when the system do not contain any electron in d-orbitals or contain all the five d-orbitals
symmetrically field then the overall energy should become equal to the bary center. So, when all
the 10 electrons are filled in the d- orbitals in the octahedral symmetry, the overall energy of the
system should become zero. For each of the electron possessing e g level energy is raised by the
value Y, while each of the electron i.e. occupied in t 2g level is stabilized by the value X. So. For
the case of 10 electrons the overall energy
4Y + 6X = 0 ……… (2)
Solving the above two equations, Y comes as +3/5 Δo and X becomes -2/5 Δo. So, each of the t 2g
orbital has 0.4Δo less energy than the bary center, or you can say each electron of t 2g orbital is
stabilized by 0.4Δo energy and each of the electron present in egorbital is destabilized by 0.6 Δo
energy. On the basis, let’s find stabilization energy for a specific octahedral case.

Crystal field stabilization energy(CFSE) = [-0.4p + 0.6q] Δo(ignoring pairing energy)

In which p is the number of electrons in t2g set, q is the number of electrons in egset
 Figure 7.3: Crystal splitting diagram for a d1 system

Crystal Field Stabilization energies (CFSE) of dx configuration (x = 0 to 10) of the central

metal ion in an octahedral complex:
CFSE is the difference in energy between the d electrons in an octahedral crystal field and the d
electrons in a spherical crystal field (isotopic field). We have already seen that the energy of t 2g
set is lowered by 2/5 Δo while that of egset is raised by 3/5 Δo. Now let us consider a dx ion
containing configuration, in which p is the number of electrons in t 2g set, q is the

number of electrons in egset and x= p+q.

Change in energy for configuration (in terms of Δ o)

= Loss in energy due to p electrons in t2g set + gain in energy due to q electrons in egset.

= (-0.4p+ 0.6q) Δo(ignoring pairing energy)……………………………….(i)

Now, sinceΔo= 10 Dq,

Change in energy for configuration (in terms of Dq)

= (-4p+ 6q) Dq(ignoring pairing energy)………………………………….(ii)

In the above equations we have not considered pairing energy, P, of dx ion, which we will learn
in the next module.

But, before that let’s solve a problem for better understanding of the concept.

The complex [Ti(H2O)6]3+ absorbs ultraviolet light at 20,300 cm-1 due to d-d transition. Find out
the crystal field splitting and crystal field stabilization energy for this system. Given that, 1
kJ/mol is identical to 83.7 cm-1.

In the complex, [Ti(H2O)6]3+ central metal ion is Ti3+, having electronic configuration
1s22s22p63s23p63d1. Therefore, d subshell occupy only one electron. According to Aufbau
principle, this goes to one of the t2g orbital. This electron of t2g on absorption of a photon of
energy 20,300 cm-1 jumps to eg level. Thus the energy 20300 cm-1 covers the value of crystal
field splitting i.e. Δo.

Therefore, Δo = 20300 cm-1 = 20300/83.7 KJ/mol = 243 KJ/mol.

Now, CFSE = (-0.4p+ 0.6q) Δo

Where p is number of electrons present in t2g shell and q is the no. of electrons present in eg
orbitals. As, you can see here, p = 1 and q = 0.

So, CFSE = (-0.4×1 + 0.6×0) Δo = -0.4Δo

Putting value of Δo in the above result, CFSE = -0.4×243 KJ/mol = 97.2 KJ/mol.