ELECTRONIC SPECTROSCOPY

This can also be called as ultraviolet-visible-near infrared

spectroscopy. This mainly deals with the electronic excitation
in molecules. The region from 200 to 1100 nm will be useful in
the study of complexes. This study helps to determine the
structure of a complex in the following ways:

 This spectrum helps to determine the oxidation state of

the central metal atom and thus the number of d-
electrons in the metal.
 The geometry of the complex like octahedral,
tetrahedral, square planar etc.

In order to arrive at these, the following steps are followed:

 The number and position of absorption maxima are

identified which in turn gives the number of transitions
in the complex.

The oxidation state of the central metal ion is determined from

the number of transitions.

 Then the geometry that is in agreement with these

transitions is proposed.

1
 In order to understand the electronic spectroscopy, the
following steps must be followed:

Electronic configuration

Terms
Term Symbol

Spectroscopic Term
Symbol
Splitting of the Terms under Various Fields
Splitting of d1 – d9 systems

Energy Level Diagram

Energy Levels and their Dependence on Crystal

Field
Orgel Diagram

Tanabe – Sugano Diagrams

Distortions: Jahn – Teller Effects

Electronic Configuration

This tells how the electrons are arranged in a certain set of

orbitals. In other words, the electronic configuration assigns a

2
given number of electrons to a certain set of orbitals. For
example, if there are six electrons in an atom, they are arranged
as 1s22s22p2. Another example is d5 system. This configuration
merely tells that there are five electrons in d-orbitals. But it
does not tell how these electrons are arranged within the
different d-orbitals.

Terms

This tells us how the given numbers of electrons are

arranged within a particular orbital and how many different
arrangements are possible. Each arrangement has its own
energy and there are different numbers of arrangement possible
from a configuration. Thus an electronic configuration gives
rise to a number of terms.

Example. Let us consider the electronic configuration d4.

This gives rise to the following arrangements:

t2g3eg1; t2g2eg2; t2g1eg3; t2g4eg0; t2g0eg4 etc.

Each one represents one energy level or term. In the above

example, we can say that the d4 electronic configuration has
given rise to five terms or five energy levels.

Term symbol

3
 The various energy levels are represented by symbols called
term symbols. The following steps derive the term symbols:

Step 1: Write the electronic configuration.

Step 2: Omit all the closed shells and sub shells.

Step 3: Determine the different electron arrangements allowed

by the Pauli exclusion principle (Pigeonhole diagram).

Step 4: Determine all the possible values of ML and MS of the

different arrangements.

Step 5: Check up with the formula

N = Nl! / {x! ( Nl – x)! }

where Nl = 2(2l+1) and x = number of electrons.

Step 6: Set up a chart of microstate consisting of one

combination of ML and MS.

Step 7: Resolve the chart of microstates in to appropriate

atomic states: (2S+1) columns and (2L+1) rows.

Step 8: Determine the J values: L+S , L+S-1, L+S-2, ………..,

|L-S|

4
Step 9: Determine the ground state by applying the three
Hund’s rules:

 2S+1 should be maximum.

 If more than one term possesses the same multiplicity,
the one with the highest L value is the ground state.

If shells are less than half-full, states with lower J value are
lower in energy.

Example 1: Carbon

Step 1: Write down the electronic configuration: 1s22s22p2

Step 2:Omit all the closed shells and sub-shells omit 1s2 and 2s2
.

Step3 & 4: Determine the different electron arrangements

allowed by the Pauli exclusion principle. Determine all the
possible values ML and MS of the different arrangements by
Pigeonhole diagram:

        
        
        

5
Step 5: Check up the arrangements with the formula, N = Nl /
{x!(Nl-x)!}; Nl = 2(2l+1); x = No. of electrons. l=1 for ‘p’
orbital. Nl = 2(2.1 + 1) = 6; x =2. N = 6! / 2!(6-2)! =
6.5.4.3.2.1 / 2.1.4.3.2.1 = 15. There are 15 columns in the
pigeon hole diagram and hence correct.

Step 6: -

Step 7: Resolve the pigeonhole arrangement in to appropriate

atomic states. The highest ML = +2. This corresponds to
symbol ‘D’. Underline ML = +2, +1, 0, -1, -2. ML = +2 appears
only once. Hence, 2S+1 = 1. Therefore, these constitute the
term 1D.

Next higher value of ML = +1; the symbol is P. ML = +1

occurs thrice. Therefore, the multiplicity is 3. Underline ML =
+1, 0, -1. Therefore, the term symbol is 3P.

Now, we are left with ML = 0. The symbol is S. ML occurs

only once. Therefore, 2S+1 = 1. Hence, the term symbol is 1S.

Thus, the pigeonhole diagram is resolved as 1D, 3P, 1S.

II Method

6
 The maximum ‘L’ value is +2. The different L values are
+2,+1,0,-1,-2. MS = +1,0,-1. Now the following table is
constructed.

MS +1 0 -1
2 1+,1-
1 1+,0+ 1+,0-; 1-,0+ 1-,0-
0 1+,-1+ 1+,-1-;1-,-1+ 1-,-1-

0+,0-
-1 -1+,0+ -1+,0-;-1-,0+ -1-,0-
-2 -1+,-1-

Resolve the above microstate chart in to appropriate atomic

states; that is, (2S+1) columns and (2L+1) rows.

(a) In the above chart, ML = 2 occurs only once. That

is, it is a singlet state. ‘2’ corresponds to the symbol ‘D’.
Therefore, the atomic state is 1D. An atomic state forms an
array of microstates consisting of 2S+1 columns and 2L+1
rows. For 1D state, 2S+1 = 1; i.e. one column. 2L+1 = 2(2) + 1
= 5 rows. These are marked and removed from the chart.
(b) ML=1 occurs thrice. Hence, it is a triplet. ‘1’
corresponds to the symbol ‘P’. Therefore, the atomic state

7
occurs in three columns; 2L+1 = 2(1)+1 = 3 rows. Again these
are marked and removed from the chart.
(c) Now, we are left with only one microstate with
ML=0. This occurs in only one column. Hence, the multiplicity
is ‘1’. ‘0’ corresponds to the symbol ‘S’. Therefore, the atomic
state is 1S. Thus the p2 configuration gives rise to three terms,
viz., 1S, 3P and 1D.

Step 7: Determination of the ‘J’ values.

J=L+S

1
D Term: 2S+1 = 1; i.e. only one ‘J’ value is possible. L = 2; S
= 0; J = L+S = 2+0 = 2.

Therefore, the term symbol is 1D2.

1
S Term: 2S+1 = 1; i.e. only one J value is possible.

L = 0; S= 0; J=L+S=0. Therefore, the term symbol is 1S0.

3
P Term: 2S+1=3. i.e. three J values are possible.

L=1; S=1; J=L+S= 1+1 =2. The possible J values are:

L+S,L+S-1,……|L-S| ; i.e. 2,1,0. The different P terms are;
3
P2,3P1,3P0

Determination of ground state:

8
 Hund’s Rule 1: 2S+1 should be a maximum. Therefore, of
the three values,1D,1S and 3P, 3P is the ground state.

Hund’s Rule 2: There are two singlet terms, viz., 1D and 1S .

The one with the highest L value has lower energy. Therefore,
1
D has lower energy than 1S. The order of the terms is:

3
P<1D<1S

1
D

3
P

Hund’s Rule 3: If shells are less than half full, states with lower
J value are lower in energy.i.e.3P0<3P1<3P2. Thus the complete
arrangement of energy levels is given below:

1 1
S …………….. S0

1 1
D …………….. D2

3
P2

3 3
P P1

3
P0

9
Example 2: d2 system:

Step 1: The electronic configuration is 1s22s22p63s23p63d2

Step 2: Omit the closed shells and sub shells. Therefore, we are
left with 3d2.

Step 3. Determine all the possible values of ML and MS.

(a) There are five ‘d’ orbitals.

+2 +1 0 -1
-2
(b) The maximum value of L is +4:



+2 +1 0 -1 -2
(c) The different values of ML are:
4,3,2,1,0,-1,-2,-3,-4.
(d) The possible spin values are:
+1 0 -1
  
Step 4: Determine all the electronic configurations allowed by
Pauli exclusion principle.

10
MS +1 0 -1
ML   
++ +- --
4 2+2-
3 2+1+ 2+1- ; 2-1+ 2-1-
2 2+0+ 2+0- ; 2-0+ 2-0-
1+1-
1 2+-1+ 2+-1-, 2--1+ 2- -1-
1+0+ 1+0- , 1-0+ 1-0-

0 2+-2+ 2+-2- ,2- -2+ 2- -2-

1+-1+ 1+-1- ,1- -1+ 1- -1+
0+0-

Step 5: Check up with the formula

N = Nl! / x!(Nl – x)!

Where Nl = 2(2l + 1); x = No. of electrons.

Nl = 2(2l + 1) = 2( 2 x 2 + 1) = 10; x = 2
N = 10! / 2!(10 –2 )!
= 10.9.8.7.6.5.4.3.2.1. / 2.1 .8.7.6.5.4.3.2.1.
= 10 x 9 / 1 x 2 = 45
There are 45 microstates in the above chart. Hence correct.

Step 6: Resolve the above microstate chart in to appropriate

atomic states; that is, 2S+ 1 columns and 2L + 1 rows. In the
above chart, ML = 4 occurs only once. Hence, it is a singlet
state. ‘4’ corresponds to the symbol ‘G’. Hence, the atomic
state is 1G. An atomic state forms an array of microstates
consisting of 2S+1 columns and 2L+1 rows. These are marked
and removed from the chart.
ML = 3 occurs thrice, i.e. in three columns. Hence, it is a
triplet state. ‘3’ corresponds to the symbol ‘F’. Therefore, the

11
atomic state is 3F. For a 3F state, there are 2S+1 = 3 columns
and 2L+1 = 7 columns (2 x 3 + 1 = 7). These are marked and
removed from the chart.
ML = 2 occurs only once, i.e. in only one column. Hence, it
is a singlet state. ‘2’ corresponds to the symbol ‘D’. Hence, the
atomic state is 1D. For a 1D state, there are one column and
2L+1, i.e., 2 x 1 + 1 = 5 rows. These are marked and removed
from the chart.
ML = 1 occurs thrice, i.e., in three columns. Hence, it is a
triplet state. ‘1’ corresponds to the symbol P and hence, the
atomic state is 3P. For a 3P state , there are 2S+1 = 3 columns
and 2L+1 = 3 rows. These are marked and removed from the
chart.
ML = 0 occurs only once, i.e., in only one column and hence
it is a singlet. ‘0’ corresponds to the symbol S and hence the
atomic state is 1S. For a 1S state, there are 2S+1 = 1 column
and 2L+1 = 1 row.
Thus the different terms are: 1G, 3P, 1D, 3P and 1S.

Step 7: Determine the J values. J = L+S.

For a 1G term, S = 0 and L = 4. L + S = 4. Since it is a singlet
state, only one ‘J’ value is possible. Therefore, the term symbol
is 1G4 .

For a 3F term, S = 1 and L = 3. L+S=4;L-S=2. The possible

‘J’ values are 4,3 and 2. Hence the different terms are 3F4,3F3
and 3F2.

J = 2 has the lowest energy since the ‘d’ level is less than half
full. Therefore, the order of the energy levels is 3F2<3F3<3F4.

For a 1D term, S = 0 and L = 2. L = S = 2. Since it is a

singlet state, there is only one J value. The term is 1D2.

In the case of a 3P term, S = 1 and L = 1. L+S=2 and L-S=0.

The possible ‘J’ values are 2,1 and 0. Since the ‘d’ level is less

12
than half full, J=0 has the lowest energy. Hence, the order of
the energy levels is 3P0<3P1<3P2.

Step 8: Determination of the ground state.

Rule 1. That state with the highest multiplicity has the
lowest energy. Therefore, 3F and 3P have lower energy than
others. Of these two states, 3F has the lowest energy because its
‘L’ value is greater. Hence the order of the terms is:
3
F<3P<1G<1D<1S
The complete arrangement of the energy levels is given below:
Degeneracy
(2S+1)(2L+1)
1
S ……. 1S0 1 x1 = 1
1
D ……. 1D2 1x5=5
1
G …….. 1G4 1x9=9
3
P2
3 3
P P1 3x3=9
3
P0

3
F4
3 3
F F3 3 x 7 = 21
3
F2

Total = 45

Degeneracy of a term:
The degeneracy of each term is given by the formula
(2S+1)(2L+1):

13
 3
F term: 3 x 7 = 21
3
P term: 3 x 3 = 09
1
G term: 1 x 9 = 09
1
D term: 1 x 5 = 05
1
S term: 1 x 1 = 01

Total = 45

Spectroscopic Terms or Molecular Terms

When atomic terms are surrounded by ligands, these terms

are split and molecular or spectroscopic terms result. In an
octahedral field, the ‘S’ and ‘P’ terms are not split. The ‘D’ and
‘F’ terms are split as shown in Figure (a) and Figure (b).

Eg A2g
T2g
D F

T2g
T1g

Figure (a) Figure (b)

Reason for splitting of the atomic terms

14
 The atomic term split due to electron interaction. In an atom,
there is no interaction between electrons in an unfilled shell.
However, in an ion, the electrons present in an unfilled shell
suffer two interactions:
(i) Inter-electronic repulsion.
(ii) Spin-orbit coupling.
Inter-electronic repulsion
The electrons in a shell repel each other. Therefore the
energy depends up on how the electrons occupy the orbitals of
the shell relative to one another.
Spin-orbit coupling
The magnetic field produced by the spin of an electron
interacts with that produced by the orbital motion of the
electron. This is called spin-orbit coupling.

Effect of inter-electronic repulsion:

The inter-electronic repulsion splits the highly degenerate
energy level of the unperturbed configuration into a number of
terms.

Effect of spin-orbit coupling:

The spin-orbit coupling splits the terms into states. These
effects are schematically represented in the Figure 1.
1
S
1
D
1
G
d2 3
P2
3
P
3
P1
3
F

terms states
Figure 1. Effect of Spin-Orbit Coupling

15
Number of states arising from terms:
The number of states arising from a term is (2S+1) or (2L+1)
whichever is smaller.
These effects are schematically represented as follows:
Electronic
configuration

Electronic repulsion
Terms
Spin-orbit coupling

States
Magnetic field

Micro states

16
Specification of a State
When a particular state arises from a term, the value of ‘J’ is
added as a subscript to the term symbol. The full symbol of a
state is:
2S+1
LJ; e.g. 3P1

Racah Parameters

The inter-electronic repulsion is responsible for the

differences in energy between the terms. It is expressed in
terms of Racah parameters B and C.

Significance of ‘B’ and ‘C’

When the terms have the same multiplicity, the Racah

parameter ‘B’ is used. When the terms have different
multiplicities, the inter-electronic repulsion is expressed by a
combination of ‘B’ and ‘C’.

Kinds of Coupling
There are two types of coupling, viz., Russell-Saunders
coupling and jj coupling. They are used depending upon the
circumstances.

RS coupling
RS coupling is used when the electronic repulsion is
greater than the spin-orbit coupling. This coupling splits each
of the terms into states. RS coupling is valid for most of the
lighter elements because the effects of spin-orbit coupling are
small in these cases. In particular, this coupling applies well to
the first transition series elements.
RS coupling does not apply the heavy elements like the
second and third transition series elements. In these cases, the
spin-orbit coupling is not small but greater than the inter-
electronic repulsion. In particular, this fails in the case of third

17
transition series elements. The degeneracy of each state
obtained by the splitting of terms is given by the formula,
(2J+1).

jj coupling
It is exactly opposite to that of RS coupling. Here, the spin-
orbit coupling is more important than the electronic repulsion.
At first, the configuration is split into levels and not terms.
The ions considered under ligand-field theory do not conform
to the jj coupling scheme.

Spin-orbit coupling parameters

Two parameters are used to describe the spin-orbit coupling.
They are:
(i) Single electron spin-orbit coupling parameter,
(ii) Parameter,

(i) Parameter,
This parameter is a property of the configuration. This
measures the strength of the interaction between the spin and
orbital angular momentum of a single electron of the
configuration. This is equal to  times the scalar product
between the spin and orbital angular momentum vectors of the
electron, viz., l.s.  is a positive quantity.

(ii) Parameter, 
This property is a property of the term. This is equal to 
times the scalar product between the spin and orbital angular
momentum of the term, viz., L.S

Relation between the two parameters

The two parameters are related as follows:

18
  =   / 2S
The ‘+’ sign holds good for a shell less than half full. The ‘-’
sign holds good for a shell more than half full.

Sign of 
 is positive for a shell less than half full and the lowest
value of ‘J’, viz., L-S lies lowest in energy.

Normal multiplet
When a term is split into a set of states of increasing value of
‘J’, it is said to be a normal multiplet.

Inverted multiplet
When the shells are more than half full,  is negative. This
inverts the diagram. In the resulting multiplet, the lowest
energy will have the highest value of ‘J’. These are
summarized in Table 1.

To find out 
The spin-orbit contribution to the energy of any level is
found out by the following expression:
½ [J (J+1)-L (L+1)-S (S+1)]
For a 3p state, when J=0;S=1;L=1. Substituting the values
we get,
½ [0-1(1+1)-1(1+1)]=1/2(-4)=-2

Slater-Condon and Racah parameters

Energies of the terms above the ground term are
determined by two electron repulsion parameters, viz., the
Condon-Shortley or Racah parameters. The two set of
repulsion parameters are related as follows:
B = F2 –5F4
C = 35F4
B and C are called Racah parameters and F’s are called Slater-
Condon parameters.

19
Advantages of Racah parameters
The separations between the terms of same multiplicity
within a configuration involve only the parameters ‘B’ and that
between different multiplicities involve both ‘B’ and ‘C’.
However, in the case of Condon-Shortley parameter,
separations between the terms of even the same multiplicity are
functions of F2 and F4.

Characteristics of d-d transitions

d-d transitions are also known as ligand field spectra. These
occur in the near i.r., visible and u.v. regions, viz., 10000 –
30000 cm-1. The lower regions are not accessible
experimentally. The higher frequencies are accessible but are
overshadowed by the charge transfer and the inter-ligand
transitions. Hence, the study of the d-d transitions is limited to
the visible regions of the spectrum.

Selection rules
1. Spin selection rule:
This rule may be stated as follows:
If the spin multiplicity changes, those transitions are not
allowed.
(e.g.) s2 s1p1 is not allowed because it is a singlet to
triplet transitions (the spin of the two electrons is +1/2.) . But if
the spin of the two electrons in the s1p1 state is +1/2 and –1/2 ,
it becomes a singlet to singlet transition and is allowed.
2. Laporte selection rule:
This rule is to be applied if a molecule has a center of
symmetry. This rule can be stated as follows:
“ If the molecule has center of symmetry, transitions within
a given set of ‘p’ or ‘d’ orbitals are Laporte forbidden. That is,
those involve only a redistribution of electrons in the given sub
shell, are Laporte forbidden.”
In other words, d-d transitions in octahedral complexes
are forbidden. Any electron transition must have l = 1. Thus
only the transitions between an even state ‘g’ and an uneven

20
state ‘u’ are allowed. That is, g to g and u to u transitions are
not allowed.
But g u and u g transitions are allowed.

Breakdown of the selection rules

Spin selection rule:
A d5 ion has high pairing energy. Even then spin
forbidden transitions are observed. But the intensities are very
low. The reason for the breakdown of the rule here is that the
spin-orbit angular momentum coupling mixes the singlet and
triplet states. Even 1% mixing of the two states makes the
ground state 99% singlet and 1% triplet. The excited state
becomes 99% triplet and 1% singlet. Now the intensity is
derived from singlet-singlet and triplet-triplet transitions. The
extent of mixing depends up on the differences in energies
between the states and spin-orbit coupling constants.
Thus, the octahedral spin-free complexes of d5 ions
(Mn2+and Fe3+) must gain whatever intensity they can through
the breakdown of the spin multiplicity rule because all the
higher excited states have different and lower multiplicity than
the ground states, viz., 6S.

Laporte selection rule:

The Laporte selection rule can be broken down by mixing of
the orbitals on the metal ion, viz., d-f or d-p or by vibronic
coupling.
Orbital mixing. The ligand vibrations may produce a
temporary distorted field and the orbitals can mix. Now the
metal atom M will not be at the center of the symmetric field
all the time during which electron transition takes place.
In tetrahedral complexes, there is no center of symmetry and
therefore d-p orbital mixing leads to more intense absorption
bands than those for the octahedral complexes.

Vibronic coupling. This is nothing but the vibrational and

electronic coupling. This removes the center of symmetry. If a

21
forbidden band lies near an allowed band, the two will mix due
to vibronic coupling and intense absorptions will be obtained.
This is called intensity stealing and depends up on the energy
differences between the two states.

Band widths and band shapes

The width of absorption bands for the d-d transitions at
room temperature is about 1000 cm-1, which is broad. The
reasons are:
(i) Molecular vibrations
(ii) Spin-orbit coupling
(iii) Jahn-Teller distortions
The multiplicity forbidden bands are sharp while the
multiplicity allowed bands are broad because the excited state
has longer bond lengths and the electronic transitions are faster
than the vibrational transitions.

d-d transition spectra

The following points must be understood in order to
understand the d-d transitions in metal complexes.
(i) Russell-Saunders states for a dn ion in the order of
increasing energies.
(ii) Group theory and quantum mechanics to find out the
effect of an external field on these states.
All the energy levels of the system must be known to explain
the spectra.

Splitting of ‘d’ orbitals in an octahedral field

The ‘d’ orbitals are split into t2g and eg sets.

The ‘s’ orbital is not split because it is spherically
symmetrical.
The ‘p’ orbitals are not split because all the three orbitals
interact to the same extent.
The ‘f’ orbitals are split into t1g, t2g and a2g sets. The splitting
of the ‘f’ orbitals is shown below:

22
 a2g

10Dq

t2g
f 2Dq
---------------------------------------------------

6Dq

t1g

The atomic states transform in an octahedral field as follows:

S ---------------------------------------- A1g

P --------------------------------------- T1g

D ---------------------------------------- T2g+Eg

F ---------------------------------------- T1g+T2g+A2g

G --------------------------------------- T1g+T2g+Eg+A1g

H ---------------------------------------- T1g+T1g+T2g+A1g

I ----------------------------------------- T1g+T2g+Eg+A1g+A2g

The low energy states for all dn configurations are S,P,D or F

and arise as shown below:

d1 and d9 ------------- 2D

d2 and d8 ------------- 3F and 3P

23
 d3 and d7 ---------------- 4F and 4P

d4 and d6 --------------- 5
D

d5 ----------------------- 6S

Hole formalism

The dn system may be viewed by means of the ‘hole

formalism’. According to this, a d9 system is described as
spherically symmetrical d10 system with a hole or missing
electron.
From this point of view, the hole behaves exactly the way
the electron does. But the difference is that, instead of finding
the lowest available orbital, the hole tends to ‘float’ to the top.
An analogous scheme for viewing such systems is to consider a
dn system as an inverted d10-n system as shown in Figure 2.
hole floats d9configninverted d1
x2-y2
eg eg

z2 b2g

xy a1g

t2g

xz,yz
b1g
hole
Figure 2 Hole formalism

24
 In other words, a d10-n configuration will behave in the same
way as the corresponding dn configuration except that all
energies of interaction with the environment will have the
opposite sign.
The following figures show the splitting for D and F terms in
an octahedral environment.
Eg A2g
6Dq 10Dq
D T2g
-4Dq F 2Dq
T2g -6Dq
T1g

Figure(a) Figure(b)

Example 1. Cu(II) – d9 ion is same as inverted d1

Eg T2g

T2g Eg

d1 d9 inverted d1

Example 2. Ni(II) – d8 ion is same as inverted d2

d2 P inverted d2 T1g(P)
A2g
10Dq
T1g(F)
T2g
F F
T2g
10Dq
T1g A2g

25
Inversion applies only to the ‘F’ states. 3F is always lower in
energy than 3P (whether from d2 or d8).

d5+n is identical to that of dn. i.e. d7 = d5+2

That is, the diagram for d7 is identical to that of d2.
d3 = d5-2. i.e. the diagram for d3 is the inverted diagram of d2.
Note: + sign indicates no inversion and ‘-’sign indicates
inversion. Always express in terms of 1 or 2 for easy
prediction. The results are shown in Table 2.
Example: Cr(III) ion.
It is a d3 ion.  d5-2 i.e. inverted d2 diagram as given below:

-- 4P 4
T1g(P)
4
T1g(F)
6Dq
4
F
2Dq
4
T2g
10Dq
4
A2g

The transitions are:

4 4
A2g T2g(1)
4 4
A2g T1g(2)
The first transition seems to be equal to 10Dq from the diagram
for the inverted ‘F’ state. The second transition would be
expected to be equal to 18Dq. But it is less than 18Dq. The
reason is that the ground state4F mixes with the excited 4P level
as shown in Figure 3.

26
Table 1 Relation between the sign of  and the multiplets

Free ion term d2( +ve) d8( -ve)

(2S+1)(2L+1) (2J+1)degenerate (L+S) lowest
degenerate (L-S) lowest
1
S (1) (1) J=0 (1)J=0
S=0
L=0
1
G (1)(9) 2(4)+1=9 J=4 (9) J=4

S=0 (1) J=0

L=4 (5)  J=2
3
P (3)(3) =9 (3) J=1
(3) - J =1
S=1 (1) -2 J=0 (5) J=2
L=1
L+S=2
1
D (1)(5)=5 (5) J=2 (5) J=2
S=0
L=2 (9) 3 J=4 -4 2
J=2
3
F (3)(7)=21 - 3
(7) - 3
S=1 (5) -4 2 3 4
L=3
J=4

27
Table 2 Energy level diagram of dn states

Confign. G.S of Confign. Energy level

Free ion of complexed diagram
ion

d1 2
D t2g1 Fig.(a)

d2 3
F t2g2 Fig.(b)

d3 4
F t2g3 Inverted Fig. (b)

d4 5
D t2g3eg1 Inverted Fig. (a)

d5 6
S t2g3eg2 No splitting

d6 5
D t2g4eg2 Fig. (a)

d7 4
F t2g5eg2 Fig. (b)

d8 3
F t2g6eg2 Inverted Fig. (b)

d9 2
D t2g6eg3 Inverted Fig. (a)

d10 1
S t2g6eg4 No Splitting

28
4
P mixing
4
T1g(P)

15B
4
T1g(F)
6Dq <18Dq
4
2Dq T2g
4
F
10Dq
4
A2g

Figure 3 Orbital mixing

The wave functions for 4T1g(F) and 4T1g(P) states have

identical symmetry. Hence, they will mix. The amount of
mixing is inversely proportional to the energy difference
between the 4F and 4P levels. This is similar to the LCAO of
two atomic orbitals giving rise to two molecular orbitals, one
having higher energy and another having a lower energy then
the contributing orbitals. Due to this mixing, the 4T1g(F) will lie
somewhat lower in energy and the 4T1g(P) will lie somewhat
higher in energy than the expected values in the absence of
mixing.

Comparison of Experimental and Theoretical data

The experimental data do not agree with the theoretical

data. Two corrections must be made in order to improve the
interpretation and correction of the spectra.

29
  The extent of mixing of the F and P terms must be
considered while calculating the energies.
 The nephelauxetic effect must also be taken into
account.
Due to nephelauxetic effect, the interionic repulsion is reduced.
Hence, the apparent value of ‘B’ is always smaller in
complexes when compared to the free ion. If B represents the
repulsion in the complex, then

 = B/B ------- (1)

 is always less than ‘1’ and decreases when the delocalisation

increases. It can be obtained from the following relation:
(1 - ) = hx.kM---------- (2)
where hx is the parameter for the ligand and kM is for the
metal.
In the case of Cr(III), if all the three transitions are
obtained, B can be found out easily by applying the following
equation:
15B = 3 + 2 - 31 -------- (3)
where 1 is the absorption occurring at the lowest frequency. If
only two transitions are observed and the third one is obscured
by a charge transfer band, B can still be calculated but more
complicated.

ORGEL DIAGRAM

The magnitude of splitting of the energy levels for an ion

is plotted against the increasing ligand field strength for a dn
system taking in to consideration the spin – orbit coupling and
mixing of the different energy states. The resulting diagram is
called the Orgel diagram for the dn ion.

In other words, Orgel diagram is the pictorial

representation of the energy level diagrams obtained by

30
incorporating the adjusted B and C values including the effect
of variable field strength. The diagram is shown in Figure 4.

Figure 4. Orgel Diagram

The Orgel diagram for the P and F states in octahedral

as well as in the tetrahedral field is shown in the Figure 4.

Characteristic features of Orgel diagram

1. Orgel diagram treats only the weak field or high –
spin case.
2. States with identical designations never cross.
3. The crystal field states have the same spin
multiplicity as the free ion states from which they
originate.

31
 4. States that are the only ones of their type have
energies that depend linearly on the crystal field
strength.
5. When there are two or more states of identical
designations, their lines in general will show
curvature because such states interact with one
another as well as with the crystal field.

Correlation diagrams and analysis of the spectra

If a spectrum is to be completely analyzed, a correlation

diagram showing all energy terms (ground as well as the
excited state) should be shown and analyzed. That is, the
following points must be taken into account:
 Free ion energy terms
 Terms in a weak field
 Variations in the field of intermediate strength
 Terms in a strong field configuration

d1 ion:
The ground term is 2D. This splits in to high energy Eg level
and low energy T2g level. The electron transition from the
lower to the upper level is a direct measure of the ligand field
strength.
2
Eg
E
2
D 10Dq

2
T2g

o
Free ion Field Strength

32
d2 ion:

When more than one electron is present, the energy levels

depend upon the following factors:
 Ligand field strength, 10Dq
 Interelctronic interaction

In the ground state, the configuration is t2g2. The two electrons

can have any one of the following arrangements:

dxy1dyz1dzx0; dxy0dyz1dzx1; dxy1dyz0dzx1

Thus, the ground state is triply degenerate. The spin
multiplicity is 2S+1 = 2(1) + 1 = 3.Thus, the state is
represented as 3T1g(F) state. When one electron is excited, the
configuration becomes t2g1eg1. There are two possibilities of
excitation. When dxz or dyz electron is excited, it can go to
either dz2 or dx2-y2 orbital. The resulting configuration will be

dxy1dyz0dzx0 (dz2)1 (dx2-y2)0 or dxy1dyz0dzx0 (dz2)0(dx2-y2)1

In the first case, the repulsion will be less and in the second
case, the repulsion will be more. Similarly, when an electron is
promoted from the dxy orbital, it will go to the dx2-y2 orbital
leaving the other electron in the dyz or dxz orbital. Thus, three
degenerate excited states exist as shown below:

dxy1(dz2)1 ; dyz1(dx2-y2)1 ; dzx1(dx2-y2)1

Put together, these three form the 3T2g(F) state.

The other degenerate arrangement is:

dxy1(dx2-y2)1 ; dyz1(dz2)1 ; dzx1(dz2)1

These three put together constitute the 3T1g(P) state.

33
 There is another arrangement, viz., t2g1 eg1 in which, the spin
of one of the electrons is reversed:

t2g eg
Now, the spin multiplicity becomes 2S + 1 = 2(0) + 1 = 1. That
is, the ground state is a triplet while the excited state is a
singlet. Therefore, the transition will be triplet to singlet. This
transition will be multiplicity forbidden.

Lastly, both the electrons may be excited to the eg level

giving the configuration eg2. One electron will be present in
each of the two eg orbitals. Thus, there is only one arrangement
possible and hence it is a singly degenerate state giving 3A2g(F)
state.

The splitting of a d2 configuration (2D term) gives rise to the

following states:
3
F, 1D, 3P, 1G and 1S.
Considering the ground state,3F and the next higher energy
state,3P, the following energy level diagram is obtained:
3 3
P A2g(F)
3
E T1g(P)
1
D
3
T2g(F)
3
F
1
T2g
3
T1g(F)


34
 The spectra of the d2 ion complexes show two transitions,
3 3
viz., T1g(F) T2g(F) and 3T1g(F) 3
T1g(P). The
transition from 3T1g(F) to 3A2g will involve the excitation of
both the electrons to the higher level and hence is not likely to
be observed.
For example, the spectrum of [V(OX)3]3- shows two
absorptions at 17000 and 24000 cm-1 corresponding to the
transitions shown in the above figure.

d3 ion:
The ground state for the d3 ion is 4F. It splits as follows:
4
A2g, 4T2g and 4T1g
Figure 3 is drawn again to show the splitting of the F and P
terms and mixing of the T1g terms from F and P levels.

4
T1g
4
P ---------
4
T1g

15B
4
F
4
T2g

1 2
4
A2g

1 = 10Dq; 2 < 18Dq

35
2 should be equal to 18Dq but it is always less than 18Dq due
to mixing of the similar 4T1g(F) and 4T1g(P) states. In general,
the transitions formulated above do not give the observed
spectral bands. This is due to
 incorrect mixing of the F and P states
 nephelauxetic effect

These values decrease the value of C and B in the complexes

when compared with the free ion values.

d4 ion:
The energy level diagram is same as inverted d1. The ground
state is 5d. This splits as follows:
5
T2g
5
D ----------------------
5
Eg

Here there is no mixing from the higher energy levels. The

transition is 5Eg 5
T2g

d5 ion:

High spin d5 ions like [Mn(H2O)6]2+ or [Fe(H2O)6]3+ are

almost colorless. The features of the spectrum are:
 The extinction coefficients are very low. Here, all the
‘d’ orbitals are singly occupied. Hence, transition of
the electron must cause spin pairing in one of the
orbitals. Thus, d-d transitions will be spin-forbidden.
 The absorption spectrum has many bands. The reason
is that, in the energy level diagram many states lie
close together. As a result, many closely spaced
multiple absorption bands appear.
 In the spectrum, two bands are sharper than the
others are. They correspond to the transitions,

36
 6 4
S Eg(G) + 4A1g and 6S 4
Eg(D). These are
not affected by ligand field strength. Hence, they are
sharp. However, in the case of other transitions, the
energy depends on the strength of the ligand field, so
that they are broadened.

d6 ion:

The ground state is 5D for the weak field case. It is similar

to d1 case. The low spin state for d6 ion is 1I. This is a high-
energy term. The energy level diagram is given below:

5
Eg
1
I
1
T2g
1
T1g
5
D
1
A1g
5
T2g

It is clear from the diagram that the 1A1g and 1T1g states are
stabilized (lowered in energy) more than the 5T2g state as the
strength of the ligand field increases. Hence, at higher field
strength the ground state of the ion becomes 1A1g.
(e.g.) cobalt(III) – d6 ion.
The spectra can be predicted easily for this ion. The high
spin complex, [CoF6]3- shows only one absorption band at
13000 cm-1 due to 5T2g 5
Eg transition, where as the
low spin cobalt(III) complex shows two peaks corresponding to

37
1 1
A1g T1g and 1A1g 1
T2g. For example, the
complex, [Co(en)3] shows transitions at 21400 and 29500cm-1
3+

and the complex, [Co(OX)3]3- at 16500 and 23800 cm-1.

d7ion:
The ground state term is 4F. When the 4P state is not too
high, the energy level diagram becomes similar to the diagram
of d2 ion.

d8 ion:
The energy level diagram of the d8 resembles that of the d2
system, but inverted. Three transitions are observed:
3 3
A2g T2g ; 3A2g 3
T1g(F) ; 3A2g 3
T1g(F)

d9ion:
This is same as a d1 system but inverted. Visible spectrum
of a d9 system in an octahedral field is rare due to Jahn – Teller
effect. In actual practice, a non-symmetric absorption band
results due to Jahn – Teller effect. The resulting distortion is
more in d9 than in the d1 system. Further, the ground state in
Cu2+ (d9) is doubly degenerate and the excited state is triply
degenerate. Hence, a broad spectrum results.

The Tanabe – Sugano Diagram

The energies of the states in terms of E/B are plotted against

Dq/B taking the ground state of the system on the x-axis. The
resulting diagram is called Tanabe – Sugano diagram.

Merits
These diagrams are applicable to both strong and weak field
cases unlike the Orgel diagram, which is applicable only to
weak field cases.
Demerits

38
  The diagrams are drawn to a specific C/B ratio and
hence not valid for all similar systems, which generally
differ in C/B ratio.
 There is no accurate way to determine C and B values
for the metal ions in complexes.
 The C and B values for the metal ions in complexes are
lower than the values for the free metal ions. However,
the Orgel and the Tanabe – Sugano diagrams do not
consider this point at all.

The transitions for the Co3+ complexes can be predicted from

the Tanabe – Sugano diagram for d6 system. Let us consider
only the transitions occurring without change in spin
multiplicity (selection rule).
For high - spin complexes, like CoF63-, only the quintet state,
5
D, will be important. Therefore, only one transition, viz.,
5 5
T2g Eg should be observed. The blue color of this
complex is due to a single peak at 13000 cm-1. For low spin
Co(III) complexes we expect two transitions, viz., 1A1g 1
T1g
1 1
and A1g A2g.

Splitting of orbitals under various symmetries

Trigonal (ligands lie in xy plane)

x2-y2 , xy 5.46

z2 -3.21

xz, yz -3.86

39
Tetrahedral

xz,yz,zx
1.78

x2-y2,z2 -2.67

Square planar (ligands lie in xy plane)

x2-y2 12.28

xy 2.28

z2 -4.28

xz,yz -5.14

Trigonal bipyramid (pyramid base in xy plane)

z2 7.07

x2-y2, xy -0.82

xz,yz -2.72

40
Square pyramid (pyramid base in xy plane)

x2-y2 9.14

z2 0.86

xy -0.86

xz, yz -4.57

Octahedron

x2-y2, xy 6.00

xy,yz,zx -4.00

41
Trigonal prism

xz,yz 5.36

z2 0.96

x2-y2,xy -5.84

Pentagonal bipyramid

z2 4.93

x2-y2,xy 2.82

xz,yz -5.28

Cube

xz,yz,zx 3.56

z2,x2-y2 -5.34

42
Square antiprism

xz,yz 3.56

x2-y2,xy -0.89

z2 -5.34

Icosahedron

All the five ‘d’ orbitals are degenerate.

Selection rules
The different colors of the transition metal ions arise from
the absorption of part of the visible spectrum by ions and their
dissociated ligand groups.
The absorption of light by complex ions takes place by the
electric dipole mechanism. In other words, complexes absorb
light by this only important mechanism. If the radiation of
frequency applied is equivalent to the energy separation
between the two energy levels, the light may be absorbed. If
the absorption is to take place by the electric dipole
mechanism, the transition moment integral, Q, must be non-
zero.
Q = < 1| r| 2>
‘r’ is the radius vector. This has the symmetry of of an electric
dipole.

Components of wave functions

A wave function may be considered a product of the

different wave functions as follows:

 = orbital . spin . vibrational . rotational . translational

43
 Except for the gas phase, the last two terms in the above
expression are not likely to change for a molecule in a time
comparable to the life times of excited electronic states. Hence,
they integrate out to unity in the expression for Q. From the
remaining part of the expression, it is clear that ‘Q’ will be
equal to zero only if
1,spin  2,spin
In other words, ‘Q’ will not be equal to zero if
1,spin = 2,spin -------------- (1)
and ,
< 1,orbital . 1,vibrational| r | 2,orbital . 2,vibrational >  0.------(2)
The first relation will be satisfied, when both the wave
functions have the same spin quantum number,S.
The radius vector,r, is antisymmetric to inversion through
the center of the system. Hence, integration of the function,
1,orbital |r | 2,orbital
from - to + yields zero if both 1 and 2 are ‘g’ or both ‘u’
in symmetry. Since the wave functions of ‘d’ orbitals have ‘g’
symmetry, ‘Q’ is zero for d-d transitions in an octahedral
complex (the vibrations are not considered).

The group theory tests whether the second relation is equal or

not equal to zero. The basic principle is that if 1 and 2
transform as the irreducible representations 1 and 2 of the
group to which the molecule belongs, and r transforms as r of
that group, then,
Q = 0, if the reducible representation 1r2 does not
contain the totally symmetric representation of that group,A1g.
Q  0, if the irreducible representation contains A1g. The radius
vector, r = x + y + z and therefore, it transforms in the same
manner as the set of Cartesian coordinates in the groups Oh and
Td. ‘r’ transforms as T1u for Oh and T2 for Td. When the
direct product does not contain A1g, the transitions are
orbitally forbidden. When the inversion properties are not

44
obeyed, the transitions are Laporte forbidden. Singlet-triplet,
quartet-doublet etc., transitions are spin – forbidden.

d1 – octahedral complex:
The M.O. diagram is shown below:

a1ga

t1ua

ega

T2g+Eg t2gn

a1g+eg+t1u

T1u
egb
xx xx

A1g

t1ub
xx xx xx

a1g
xx

(  - bonding only)

x – denotes ligand paired electrons

- denotes metal ‘d’ electrons

45
Excitation of the ‘d’ electron from the t2gn molecular orbital to
the ega or the a1ga molecular orbitals is forbidden because each
has subscript ‘g’.

When the transition to the t1u orbital is considered, it is

governed by the direct product,
T2g x T1u x T1u

Ground state nature of ‘r’ state to which e- is excited

The character table for ‘O’ group is given below:

O E 6C4 3C2(=C42) 8C3 6C2

A1 1 1 1 1 1

A2 1 -1 1 1 -1

E 2 0 2 -1 0

T1 3 1 -1 0 -1

T2 3 -1 -1 0 1

T2 = 3 -1 -1 0 1

T1 = 3 1 -1 0 -1

T1 = 3 1 -1 0 -1

T2xT1xT1 = 27 -1 -1 0 1

46
The above reducible representation is reduced as follows:

A1 = 1/24[(27.1.1)+(-1.6.1)+(-1.3.1)+(0.8.1)+(1.6.1)]
=1
A2 = 1/24[(27.1.1)+(-1.6.-1)+(-1.-3.-1)+(0.8.0)+(1.6.-1)]
=1
E = 1/24[(27.1.2)+(-1.6.0)+(-1.3.2)+(0.8.-1)+(1.6.0)]
=2
T1 = 1/24[(27.1.3)+(-1.6.1)+(-1.3.-1)+(0.8.0)+(1.6.-1)]
= 3
T2 = 1/24[(27.1.3)+(-1.6.-1)+(-1.3.-1)+(0.8.0)+(1.6.1)]
= 4
Therefore, T2g.T1u.T1u = A1g+A2g+2Eg+3T1g+4T2g

Thus, the reducible representation contains A1g and therefore,

the transition is allowed. This transition is not purely d-d
transition and contains some charge transfer character.

Molecular Orbital Diagrams for -bonding in Tetrahedral

Complexes

a1a

t2 t2 a

a1

10Dq t2+a1

t2 +e en

t2 b
xxxxxx
a1b
xx

47
The symmetry of the ‘p’ orbitals is t1u. It transforms as t2 in a
tetrahedral field.

‘x’ denotes ligand paired electrons

denotes metal ‘d’ electrons

The transition is en to t2a. These transitions are largely of the

ligand field type. The integral is <en|r|t2a>
r = x+y+z transforms as t2 in tetrahedral field. Therefore, the
integral is <E.T2.T2>.
The direct product,
E x T2 x T2 = 2T1+2T2+2E+A2+A1
This contains A1. However, the inversion properties(g or u)
have not been investigated. Hence, the presence of A1 alone is
not sufficient to establish the existence of the matrix element
<en|r|t2a>

Although the molecular orbitals in a tetrahedral complex do

not possess g or u properties, but the atomic orbitals out of
which they are constructed do possess. The en molecular orbital
is composed of metal d orbitals only, while the t2a molecular
orbital may contain both d and p atomic orbitals of the metal
ion. The d orbitals have g character, while the p orbitals have u
character.
That part of the integral, which involves the d orbital
contribution to the t2a molecular orbital must vanish, but that
part, which involves the p orbitals may be non – zero. Hence,
the ligand field transitions, which are forbidden in octahedral
complexes, may be partially allowed in tetrahedral complexes
because of d-p mixing.

48
Break down of selection rules

If the spin and Laporte selection rules were rigorously obeyed,

only a few absorption bands would be observed for transition
metal complexes. However, neither of the rules holds very
strictly because some mechanisms offer relaxation.

Spin selection rule break down

This rule is not fully valid in the presence of spin – orbit

coupling. The coupling between spin and orbital angular
momenta within an ion factorizes the total wave function
accurately in to spin and orbital wave function products.
However, the factorization can only be approximate. Hence,
the spin selection rule cannot be strict. Therefore, the spin –
forbidden bands appear in the transition metal complexes.
However, the intensity is one or two orders of magnitude less
than that of the allowed transitions.

The intensity of spin – forbidden bands relative to spin –

allowed bands increases as spin – orbit coupling constants
increase. The spin – orbit coupling increases as one moves to
the right hand side of a transition series, or from the first to the
third transition series within a group of the periodic table.

Laporte selection rule break down

This rule can be broken down in two ways:

1. Vibronic coupling
2. Reduction of symmetry

Vibronic coupling

The Laporte selection rule assumes that vibrations are

absent. However, the ligand atoms of a complex do vibrate.
Therefore, a suitable combination of vibrations in the ground

49
and the excited electronic levels relaxes the rules. The coupling
between electronic and vibrational wave functions is called
‘vibronic’. The vibronic wave function has symmetric
representations determined by the direct product of the
representations of electronic and vibronic.

In general, there are a number of possible modes of

vibration to the ground and excited terms of a complex. It is
almost certain that for some vibrations,
1,vibronic.r.2,vibronic
contains A1g and hence the integral,

<1,vibronic.|r|2,vibronic>  0
Therefore, the transition between 1 and 2 is allowed to at
least some extent. For example, in an octahedral complex, and
considering only d-d transitions, if the ground term is mixed
with a g – type vibration, the excited term must be mixed with
a u – type vibration and vice-versa. Laporte – forbidden bands
are usually three orders of magnitude or more weaker than
allowed transitions.

Reduction of symmetry

This also causes relaxation in selection rule. For example,

consider reduction of cubic symmetry. Consider the 3T1g to
3
A2g transition of the d2 configuration. The transition moment
integral is:
<T1g.T1u.A2g>
The direct product in the group, Oh is:
T1g x T1u x A2g

T1 x T1 = A1+E+T1+T2
gxu=u
Therefore, T1g x T1u = A1u+Eu+T1u+T2u

T1g x T1u x A2g = [A1u+Eu+T1u+T2u]A2g

50
A1u x A2g = A2u
Eu x A2g = Eu
T1u x A2g = T2u
T2u x A2g = T1u

Hence, T1g x T1u x A2g = A2u + Eu + T2u + T1u

Thus, the direct product does not contain A1g or even A1 if the
inversion properties are ignored. Consequently, the transition is
doubly forbidden by the symmetry of the electronic wave
function.

Suppose, now the octahedron is distorted by compression or

elongation along the z-axis. The resultant figure belongs to the
Group D4h. The irreducible representation T1g of the group Oh
must correspond to other irreducible representations of the
Group D4h, since there is no triply degenerate irreducible
representation in that group. T1g in Oh corresponds to A2g+Eg in
D4h, and T1u corresponds to A2u+Eu. A2g in Oh corresponds to
B1g in D4h. The correlation is given in Table 3. Now, the direct
product
T1g x T1u x A2g = (A2g + Eg)(A2u + Eu)(B1g)
The second term in the product is concerned with the selection
rule for Qx,y and is
A1u+A2u+B1u+B2u+Eu
The first term is concerned with Qz and is Eu+B1u
From these results, it is deduced that the reduction in
symmetry from Oh to D4h partially relaxes the orbital selection
rule for radiation incident in the plane of the molecule (xy-
plane) because the direct product of the representation of the
ground and excited terms with that of the transition moment in
the plane, Qx,y, contains the A1 irreducible representation.
However, the rule is not relaxed for the radiation down the C4
(z) axis of the molecule.
In other words, the transition is no longer as forbidden as it
was in cubic symmetry, and is anisotropic. An absorption band
corresponding to the transition is polarized. The reduction in

51
symmetry has no effect on the inversion properties of the wave
functions, and so the transition is still Laporte forbidden. The
Laporte selection rule must be overcome by some other
mechanism like vibronic coupling.

Band Intensities

Intensity of a band is measured in terms of oscillator

strength, f. ‘f’ is the area under the band in a plot of extinction
coefficient,, versus frequency, . Very often, the intensities
are compared by means of their extinction coefficients. The
intensities of various types of transition in metal complexes are
given below:
Type of transition App.f App. 
Spin-forbidden, Laporte forbidden 10-7 10-1
Spin – allowed, Laporte forbidden 10-5 10
-3
Spin-allowed, Laporte forbidden, but with 10 102
d-p mixing (Td symmetry)
Spin-allowed, Laporte forbidden, but with 10-2 103
Intensity stealing
Spin-allowed, Laporte allowed (CT) 10-1 104

Band Widths

If the terms of the transition metal complexes correspond to

a single energy level, then the absorption bands in the spectra
should be exceedingly narrow. However, actually the bands at
room temperature and in solution are mostly rather wide
(1000cm-1). This means that the terms themselves are spread
over a comparable range of energies (that is, non-degenerate).
Several factors are responsible for lifting the degeneracies of

52
terms. Some or all of them may operate together in any
particular situation. The important factors are:
 Vibration
 Spin-orbit coupling
 Jahn-Teller effect

Vibration

Actually, 10Dq depends upon the metal – ligand separation.

Vibrations modulate the ligand field magnitude. Hence, they
spread energy of each term over a range of values. If the
transition is between two terms, whose energies depend upon
10Dq in different manners, then the energy of transition is
spread over a range, and the corresponding band is of
considerable width. Bandwidths of up to about 1000cm-1 may
be accounted for in this way.
In certain instances, the energies of some excited states run
parallel to the ground term, at least over a part of the diagram.
In such regions, transitions to these excited terms are
independent of 10Dq, and hence the magnitude of the ligand
field. These are not broadened by the vibrational mechanism.

Absence of vibrational fine structure

If vibrational interaction were the only band

broadening mechanism, the vibrational fine structure should
have been observed instead of a single broad band.
Nevertheless, in solution and at room temperature,
interaction with the solvent occurs and many vibrational levels
are thermally accessible. Hence, it is mostly difficult to resolve
the fine structure. All that is observed is the envelope of the
fine structure line, leading to a singlewide absorption peak.
In solid state and at low temperatures, it is possible to
resolve the fine structure in a great many bands. The reason is
that as the temperature is lowered, fewer vibrational levels are
occupied. Consequently, the chance that there are suitable

53
vibrations that couple the ground and excited terms are
reduced.
Generally, for the Laporte forbidden transitions, band
intensities depend on vibrational coupling. Hence, as the
temperature is lowered, intensities decrease.

Spin- Orbit Coupling

T terms are split by spin – orbit coupling. The energy

difference between the highest and lowest states of a term is
the ‘overall multiplet width’. For the first transition series, this
will be in the range 100 to 1000cm-1. The exact value depends
up on the ion.
The spin – orbit coupling could be observed as a fine
structure to bands under ideal conditions. However, in solution
and at room temperature, it is not possible to observe the fine
structure with the first transition elements because the spin –
orbit coupling is small. In the case of second and third
transition series, the spin – orbit coupling is large. Hence, the
fine structure has been observed in solutions of their
complexes.
The spin – orbit coupling fine structure may be resolved
even in the complexes of the ions of the first transition series in
the solid state and particularly at low temperatures.

Jahn – Teller Effect

Due to distortion from cubic symmetry (Oh and Td),

additional energy levels are seen in the spectrum. If these
levels are close, broad bands appear. That is, bandwidth
increases.

These three mechanisms are sufficient to account for the

widths of the ligand field bands in the spectra of almost all
transition metal complexes.

54
 Charge transfer bands tend to be much broader than 1000
cm-1. The reason is that transitions from the ground state to a
set of excited terms occur rather than to just a single term.

Band Shapes

The shapes of the bands are determined by three factors:

 Vibrational Interaction
 Spin – orbit Coupling
 Low symmetry ligand fields

Vibrational Interaction
This leads to asymmetrically shaped bands. The
intensities of transitions between vibrational levels increase as
the temperature increases. Therefore, if the intensity is largely
due to vibronic coupling, the symmetry is expected only at low
temperatures. At higher temperatures, a trail towards low
frequency is expected because higher vibrational levels are
occupied according to Boltzmann distribution. The position of
the band maximum may change with temperature. The band
maximum need not represent exactly the electronic energy
difference between the ground and excited terms.

Spin – Orbit Coupling

In most of the cases, spin – orbit coupling does not
split a term symmetrically. Hence, bands are expected to be
asymmetric in shape.

Low – Symmetry ligand fields

Low – symmetry ligand fields split E and T terms. The
T term may be split into two components. One component will
be of two-fold degeneracy and the other component non –
degenerate. The two components will have different energy.
Therefore, E and T terms may lead to asymmetric bands if the
orbital degeneracy is lifted by any factor.

55
 In spite of these factors, in solution, bands in the spectra of
transition metal complexes are most often symmetrical in
shape. The reason may be that all the three factors operate
simultaneously to give an average result, which is almost
asymmetric.

Diffuse Reflectance Spectrum

When the complex is insoluble in any of the solvents, the
spectrum is recorded in the solid state using diffuse reflectance
accessory. The sample is ground intimately with a suitable inert
white material, like MgCO3. The light reflected from it is
examined. The minima in the reflected light correspond to the
maximum absorptions in the complex. If the grinding is not
thorough, bands will be broader.

Colors and Range

The colors of the visible spectrum correspond to energy in

roughly the following manner:
Red 14000 – 16000 cm-1
Yellow 18000 cm-1
Green 20000 cm-1
Blue 21000 – 25000 cm-1
Violet 25000 cm-1
An absorption band in one part of the spectrum gives the
solution its complementary color. For example, a band in the
red region leads to a blue solution.

Absorbed Color Complementary Color

Violet Yellow – green

Blue Yellow
Green – Blue Orange – Red
Green Purple
Yellow – Green Violet

56
 Yellow Blue
Orange Green – Blue
Red Blue – Green

Table 3 – Correlation Table for Oh Group

Oh O Td D4h D2d C4v C2v D3d D3 C2h

A1g A1 A1 A1g A1 A1 A1 A1g A1 Ag
A2g A2 A2 B1g B1 B1 A2 A2g A2 Bg
Eg E E A1g+B1g A1+B1 A1+B1 A1+A2 Eg E Ag+Bg
T1g T1 T1 A2g+Eg A2+E A2+E A2+B1+B2 A2g+Eg A2+E Ag+2Bg
T2g T2 T2 B2g+Eg B2+E B2+E A1+B1+B2 A1g+Eg A1+E 2Ag+Bg
A1u A1 A2 A1u B1 A2 A2 A1u A1 Au
A2u A2 A1 B1u A1 B2 A1 A2u A2 Bu
Eu E E A1u+B1u A1+B1 A2+B2 A1+A2 Eu E Au+Bu
T1u T1 T2 A2u+Eu B2+E A1+E A1+B1+B2 A2u+Eu A2+E Au+2Bu
T2u T2 T1 B2u+Eu A2+E B1+E A2+B1+B2 A1u+Eu A1+E 2Au+Bu

Calculation of 10Dq, B and Assignment of Bands

d2 ion
For example, consider an aqueous solution of trivalent
vanadium salt. The color of these salts will be green. The
spectrum consists of wide band at 17200 and 25600 cm-1. V3+
is a d2 system. Based on the Tanabe – Sugano diagram for d2
configuration, the bands are assigned as follows:
3
T1g (F)  3T2g (F) ------- 17200 cm-1
3
T1g (F)  3T1g(P) -------- 25000 cm-1
The ratio between these two transitions is:
3
T1g (F)  3T1g(P) 25000
= = 1.49
3 3
T1g (F)  T2g(F) 17200

57
From the Tanabe – Sugano diagram, Dq/B (x –axis)
corresponding to this ratio of 1.49 is found to be 2.8.
Perpendiculars are drawn from this point on the x – axis. The
perpendicular cuts the lines for the 3T2g (F) and 3T1g(P) terms
corresponding to the values of E/B = 25.9 and 38.7
respectively.
For the transition, 3T1g(F)  3T2g(F), E/B = 25.9 and E =
17200 cm-1. Therefore, B = 17200/25.9 = 664 cm-1.
Substituting this value of ‘B’ in Dq/B = 2.8, we get,
Dq = 2.8B
= 2.8 x 664 cm-1
= 1859 cm-1
Therefore, 10Dq = 18590 cm-1
The ‘B’ value for V3+ ion is 860 cm-1. However, in the
complex, it is found to be 664 cm-1. Thus there is reduction in
the value of ‘B’ in the complex. Hence, the assignment of
bands is correct.

d8, Ni2+ ion

Aqueous solutions of bivalent nickel salts have a light gren
color. This is due to the presence of weak absorptions in the
red and blue portions of the visible spectrum. The bands are
found at 8700, 14500 and 25300 cm-1. These bands are
assigned as follows with the help of Tanabe – Sugano diagram
for d8 system.
3
A2g(F)  3T2g(F) ( = 10Dq) ----- 8700 cm-1
3
A2g(F)  3T1g(F) ----------------14500 cm-1
3
A2g(F)  3T1g(P) ---------------- 25300 cm-1
The ratio,
3
A2g(F)  3T1g(P) 25300
= = 1.74
3 3
A2g(F)  T1g(F) 14500
Dq/B corresponding to this ratio is obtained at Dq/B = 0.98
from the Tanabe – Sugano diagram. The vertical line drawn
from this point cuts the 3T1g(F) term at 16.
14500/B = 16

58
Therefore, B = 14500/16 = 906 cm-1
Dq/B = 0.98
Dq = 0.98 x B
= 0.98 x 906
= 888 cm-1
10Dq = 8880 cm-1
Observed 10Dq = 8879 cm-1
The ‘B’ value for Ni2+ ion = 1040 cm-1
The ‘B’ value in the complex = 906 cm-1
% reduction = 906/1040 x 100 = 87
That is, there is a reduction of ‘B’ to about 90% in the
complex.

d3, Chromium(III) ion

The aqueous solution of trivalent chromium gives a light
green color. The color is due to the absorption in the yellow
and blue parts of the spectrum.
The absorption spectrum shows bands at 17000, 24000 and
37000 cm-1 (weak band). Based on the Tanabe – Sugano
diagram ford3, the assignments are made as follows:
4
A2g(F)  4T2g(F) = 10Dq ----- 17000 cm-1
4
A2g(F)  4T1g(F) --------------- 24000 cm-1
4
A2g(F)  4T1g(F) -------------- 37000 cm-1
The ratio of any of these two bands is fitted to the appropriate
figure. The fit occurs for the lower two bands, which are the
more obvious in the spectrum, for Dq/B = 2.45.
4
A2g(F)  4T2g(F)
= 24.5 = 17000/B
B
B = 695 cm-1
10Dq = 17000 cm-1
‘B’ is reduced to about 70% of the free – ion value for Cr3+
(1030 cm-1)

d7, Co2+

59
 Aqueous solutions of the Co2+ are pink. There is a weak
absorption at 8000 cm-1 and in the region of 16000 to 22000
cm-1. Magnetic susceptibility studies show that the ground term
of cobalt(II) ion solutions in water is a quartet. Hence, the left
hand side of the Tanabe – Sugano diagram should be
consulted. The bands are assigned as follows:
4
T1g(F)  4T2g(F) -------- 8000 cm-1
4
T1g(F)  4A2g(F) -------- 19600 cm-1
4
T1g(F)  4T1g(P) --------- 21600 cm-1
The ratio of the energies of the upper and lower bands is the
most sensitive one to fit to the appropriate diagram. The ratio =
2.7. It corresponds to Dq/B = 0.96. The vertical line drawn
from this point cuts the 4T2g(F) term at 8.2. Therefore,
4
T1g(F)  4T2g(F)
= 8.2
B
8000/B = 8.2
B = 980 cm-1
10Dq = 9800 cm-1
‘B’ in the complex is reduced to about 80% of the free ion
value for Co2+ (1120 cm-1).

d4, Cr2+
Aqueous solutions of Cr2+ is present are pale blue. There is a
weak band at 14100 cm-1. From the magnetic studies, it is
deduced that Cr2+ in these cases has the quintet ground term (d4
high spin). The band is assigned to 5Eg  5T2g.

d6, Fe2+

The aqueous solution gives a pale green color, which is due

to the result of a weak absorption band in the red region, at
10000 cm-1. The ground term is known to be quintet from
magnetic studies so that left hand side of the Tanabe – Sugano
diagram is considered. The band is assigned to the spin –

60
allowed transition 5T2g  5Eg. This corresponds to 10Dq.
Therefore, 10Dq = 10000 cm-1.

d5, Mn2+, Fe3+

The color of aqueous solutions, which contain the
manganous ion, is very pale pink. The absorption spectrum of
the solutions shows a series of very weak narrower bands
stretching through the green and blue portions of the visible
spectrum and into the ultraviolet. Magnetic studies show that
the ground term of the manganous ion in aqueous solution is
sextet. The only sextet term of the d5 configuration in
octahedral symmetry is the 6A1g. Hence, there can be no spin –
allowed transitions. The bands are assigned as follows:
6
A1g  4T1g(G) -------- 18000 cm-1
6
A1g  4T2g(G) -------- 22900 cm-1
6
A1g  4Eg(G) --------- 24900 cm-1
6
A1g  4A1g(G) --------25150 cm-1
6
A1g  4T2g(D) ------- 27900 cm-1
6
A1g  4Eg(D) -------- 29700 cm-1
6
A1g  4T1g(P) --------32400 cm-1
The set of bands fit such an assignment for Dq/B = 1.1
From the Tanabe – Sugano diagram,
6
A1g  4T1g(G)
= 24.0 = 18600/B

B
B = 770 cm-1; 10Dq = 8500 cm-1

61
‘B’ is reduced to about 80% of the free ion value for Mn2+ (960
cm-1). The narrowness of some of the bands can be explained
as follows:
Energies of the 4Eg(G) and 4A1g(G) terms do not change
much relative to the 6A1g ground term as Dq changes.
Consequently, bands corresponding to transitions between the
ground term and these two terms are not appreciably broadened
by vibronic coupling. Spin – Orbit coupling also do not cause
any broadening since it does not raise the degeneracy of any of
the terms concerned.

d1, Ti3+
Aqueous solutions have purple color. Hence, green color is
absorbed. Therefore, absorption band near 20000 cm-1 should
appear. Actually, the band is located at 20300 cm-1. This is
assigned to 2T2g  2Eg = 10Dq.

62