Subject Chemistry

Paper No and Title Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding,

Electronic Spectra and Magnetic Properties of Transition
Metal Complexes)
Module No and Title 15. Electronic spectra of coordination complexes VII

Module Tag CHE_P7_M15

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 15: Electronic spectra of coordination complexes VII
 TABLE OF CONTENTS
1. Learning outcomes

2. Introduction

3. Understanding Tanabe-Sugano diagrams

3.1 Important features

3.2 Interpretation of the spectra

3.2.1 d1 configuration

3.2.2 d2 configurtion

3.2.3 d3 configuration

5. Summary

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 15: Electronic spectra of coordination complexes VII
 1. Learning Outcomes
After studying this module you shall be able to

 Know the importance of Tanabe-Sugano diagrams

 Learn the interpretation of the Tanabe-Sugano diagrams
 Identify the parameters involved in calculation of energy for the transitions
 Analyze various type of transitions feasible in the complexes

2. Introduction

What is Tanabe-Sugano diagram?

Tanabe-Sugano diagrams are a special class of

correlation diagrams in which the lowest
energy free ion term is plotted as X-axis and
all the other terms are plotted relative to this
lowest energy term. They plot energy of
different groups of degenerate electronic states
as a function of ligand field strength. The
parameter B is the Racah parameter which is
the repulsion term which arises due to the
repulsion between the terms of same spin
multiplicity. The ordinate is represented as E/B
and abscissa is given as Δ/B. these diagrams
can be qualitative as well as quantitative in
nature but mostly the results drawn are
qualitative in nature. In cases where both high
spin as well as low spin complexation is
possible that is cases of d4, d5, d6 and d7
electronic configurations a vertical line is
drawn in the middle of the diagram in order to Figure 1. Representation of Tanabe-Sugano
diagram
separate the high spin complexes from the low
spin one. The general Tanabe Sugano diagram can be represented in figure 1.

3. Understanding Tanabe-Sugano diagrams

3.1 Important features

These are special type of correlation diagrams have some important features which have to be
analyzed in order to completely interpret them and understand their importance in understanding
the electronic spectra of the coordination complexes. These features are given below.

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 15: Electronic spectra of coordination complexes VII
 1) In these diagrams the lowest energy term which is the ground free energy term is plotted on the
horizontal axis that is abscissa or X-axis.

2) The excited states are also represented above ground state term according to their increasing
energy levels

3) The energy above horizontal X-axis directly represents the energy of excited states above the
ground free energy term or we can say it shows the amount of energy by which excited states are
destabilized in comparison to the ground state.

4) The free energy terms in absence of ligand field are represented on the left and the strong field
ligand terms on the extreme right. The two extremes are joined with the help of lines depicting
the change as we go from no field towards the high field conditions. In between we can have the
weak field cases.

5) Generally, weak and strong field cases are separated in between the diagram by a vertical line
which divides the two possible orientations. At the dividing line ground state also changes.

6) Various parameters represented on the X and Y axes are stated as follows:-

(a) On the X-axis Δo/B where Δo is the octahedral ligand field splitting parameter is represented
which increases in the value as we move from left to right in the diagram.

(b) On the Y-axis E/B where E is the energy of the excited states above the ground state term is
represented. Its value increases on moving up from down along the vertical distance.

(c) B represents the Racah parameter which is the repulsion parameter that measures the extent of
repulsion between the terms of same spin multiplicity.

7) The lines joining the free ion terms and ligand field terms follow non-crossing rule according
to which terms of same symmetry do not cross each other.

3.2 Interpretation of the spectra

The Tanabe Sugano diagrams are very useful in interpreting the electronic spectrum of
coordination compounds. For various electronic configuration, Tanabe-Sugano diagrams are
drawn which will be discussed under the following heading along with important features of each
configuration.

3.2.1 d1 configuration

For the d1 electronic configuration number of electrons is one and thus the Tanabe Sugano
diagram is also quite simple to be drawn and interpret. The configuration can be represented as

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 15: Electronic spectra of coordination complexes VII
 t2g1 eg0. Now the excitation of the electron from the lower t2g level to the upper eg level forms the
excited state. The spin multiplicity of the ground and excited state is same and hence the
transition from ground to the excited state is spin allowed transition. The examples of the d1
configuration include [Ti(H2O)6]3+, [Cr(H2O)6]2+, [Cu(H2O)6]2+ etc. The Tanabe-Sugano diagram
along with the absorption spectrum can be represented as follows (figure 2). From the figure it
can be seen that only one transition is possible from the ground 2T2g to the excited 2Eg state, thus
only one transition band should be observed corresponding to the value of Δo. But in actual
practice, a single absorption band split up into two as can be seen from the absorption spectrum
(figure 2). This actually occurs due to the Jahn-Teller distortion which leads to splitting of the
single band into two. Also, it can be seen that no Racah parameter is involved in the diagram
since only single excited state is possible.

Figure 2. Tanabe-Sugano diagram and absorption spectrum for the d1 configuration

3.2.2 d2 configuration

For d2 configuration, the Tanabe-Sugano diagram is a bit complicated as compared to d1

configuration. In this case the free ion term of ground state is 3F which splits up into three states
of same spin multiplicity, namely 3T1g, 3T2g and 3A2g. The next higher term of same spin
multiplicity is 3P which transforms as 3A2g in presence of the ligand field. Since the configuration
in the weak as well as strong field is same, the diagram is only in terms of ligand field
irrespective of the applied weak or strong field. The Tanabe-Sugano diagram for the d2
configuration along with absorption spectrum is shown below (figure 3).

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 15: Electronic spectra of coordination complexes VII
 An example of d2 configuration is shown by the complex [V(H2O)6]3+. Its electronic spectrum is
shown in figure 3. Under ordinary condition the most populated state is the ground state 3T2g(F).
The excitation leads to three spin allowed absorption bands namely υ1, υ2 and υ3 as given in the
diagram. These transitions are as follows

Figure 3. Tanabe-Sugano diagram and absorption spectrum for the d2 configuration

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 15: Electronic spectra of coordination complexes VII
 From the absorption spectrum it can be seen that only two transitions are observed corresponding
to υ1 and υ2 at 17,800 and 25,700 cm-1. The third band υ3 lies at 38,000 cm-1 which is out of the
scale for the spectrum and is mostly overwhelmed by the
charge transfer bands in that region. Now in order to determine
the value of Δo from the spectrum, we have to take in
consideration the fact that the terms of same symmetry and
multiplicity tend to mix with each other and thus we can say
that there occurs a mixing of 3T1g(F) and 3T1g(P). Because of
this the lines connecting these two states with free ion terms
tend to be slightly curved than expected. Hence the value of Δo
cannot be simply determined by just determining the value of
υ1. The alternate method is to find difference between the states
with t2g1eg1 and t2g0eg2 electronic configurations. Thus the value
of Δo is the difference of energy between 3A2g and 3T2g. This
can be represented as follows (figure 4). The intricacy with this
concept is that lines of 3T1g(P) and 3A2g cross each other.
Moreover, because of this the band positions alter in the weak
and strong field cases. Hence it becomes very difficult to Figure 4. Splitting of the
understand exact position of the transitions and thus value of ground state free ion term
splitting parameter. In this kind of complicated situation, it is for the d2 configuration
better to first determine the value of Racah parameter and then
using that conclude the value of ligand field splitting parameter
Δo. Here we will take d2 case of [V(H2O)6]3+ complex for which the value of υ1 and υ2 is 17,800
and 25,700 cm-1 these correspond to the transitions from 3T1g(F) to 3T2g(F) and from 3T1g(F) to
3
T1g(P). Now we will determine the value of (υ2/υ1) which in this case comes out to be

(υ2/υ1) = (25,700/17,800) cm-1 = 1.44

From the Tanabe-Sugano diagram it can be seen that the ratio of (υ3/υ1) comes out to be
approximately equal to 2, hence the value of 1.44 definitely corresponds to the ratio of (υ2/υ1).
The ratio varies as a function of the value of Δo, hence a plot can be drawn between (Δo/B) and
(υ2/υ1). The plot can be shown as follows (figure 5)

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 15: Electronic spectra of coordination complexes VII
 Figure 5: Plot between (Δo/B) and (υ2/υ1) in order to determine the value of B for the d2 configuration

From the figure it can be seen that when the value of (υ 2/υ1) is 1.44, the value of (Δo/B) is 31.
Now by looking at the Tanabe-Sugano diagram, it can be observed that when (Δo/B) is 31, the
value of (E/B),υ1 is ≈29. Thus E/B = 29, where E is 17,800 cm-1.

(E/B) = 29; (17,800/B) = 29

Thus B = 17.800/ 29 = 610cm-1

Thus Δo = B X 31 = 19,000 cm-1

Hence the value of the Δo for the complex comes out to be 19,000 cm-1.

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 15: Electronic spectra of coordination complexes VII
 3.2.3 d3 configuration

For d3 configuration the electronic arrangement in the weak as well as strong field is t2g3 eg0 as the
ground electronic state. In the excited state an electron from the lower t2g level is shifted to the eg
level, thus the configuration changes to t2g2 eg1. The ground state has F as the lowest energy term
which in the presence of ligand field splits into A2g, T2g and T1g. The difference between the two
lowest energy terms corresponds to the value of Δo. Therefore, in order to find the value of Δo we
simply have to determine energy difference between the A2g and T2g states. The Tanabe-Sugano
diagram for this configuration can be represented as follows (figure 6). Examples of this
electronic configuration include [Cr(H2O)6]3+.

Figure 6: Tanabe-Sugano diagram and absorption spectrum for the d3 configuration

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 15: Electronic spectra of coordination complexes VII
 5. Summary
 Tanabe-Sugano diagrams are special class of correlation diagrams in which the lowest
energy free ion term is plotted as X-axis and all the other terms are hence plotted relative
to this lowest energy term.
 Tanabe-Sugano diagrams plot energy of different groups of degenerate electronic states
as a function of ligand field strength.
 The free energy terms in the absence of ligand field are represented on the left and while
strong field terms on the extreme right.
 Δo/B is represented on the X-axis where Δo is the ligand field splitting parameter which
increases in the value as we move from left to right in the diagram.
 E/B is represented on the Y-axis where E is the energy of excited states above the ground
state term. Its value increases on moving up from down along the vertical distance.
 B represents the Racah parameter which is the repulsion parameter that measures the
extend of repulsion between the terms of same spin multiplicity.
 The lines joining the free ion and ligand field terms follow the non-crossing rule
according to which terms of the same symmetry do not cross each other.
 In case of d1 configuration, only one transition is possible from the found 2T2g state to the
excited 2Eg state, thus only one transition band should be observed corresponding to the
value of Δo. But actually two bands can be seen because of the Jahn-Teller distortion
which leads to splitting of the single band into two.
 For the d2 configuration, the Tanabe-Sugano diagram is a bit complicated as compared to
d1 configuration.
 In d2 case the free ion term of ground state is 3F which split up into three states of same
spin multiplicity namely 3T1g, 3T2g and 3A2g. The next higher term of same spin
multiplicity is 3P which transforms as 3A2g in the presence of the ligand field.
 Under ordinary conditions the most populated state is the ground state 3T2g(F). The
excitation leads to three spin allowed absorption bands namely υ1, υ2 and υ3 as given in
the diagram. These transitions are as follows

 There occurs a mixing of 3T1g(F) and 3T1g(P) states. Because of this the lines tend to
be slightly curved than expected. Hence the value of Δo cannot be simply determined
by just determining the value υ1.

CHEMISTRY Paper 7: Inorganic Chemistry-II (Metal-Ligand Bonding, Electronic Spectra

and Magnetic Properties of Transition Metal Complexes)
Module 15: Electronic spectra of coordination complexes VII