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Electronic Spectra
CoF6– Co(NH3)63+ Co(CN)3+
6
of Transition Metal
High spin Low spin Low spin Complexes
4.1. INTRODUCTION
Electronic spectra of transition metal complexes help us to gain an insight into the structure and
bonding in these compounds. A very exciting characteristic of transition metal complexes is that they
exhibit colours of varying intensity throughout the visible range. A blue solution of copper sulphate
becomes dark blue on addition of ammonia solution. Perhaps the nature of the ligand has something
to do about it. The stronger NH3 ligands replace the H2O ligands. Sometimes the same metal displays
different colours even with the same ligands in different crystal fields. For example, cobalt (II) forms
pink [Co(NH3)6 ]2+ in octahedral field but blue [CoCl4]2– in tetrahedral field. Blood that flows in
our body is red because of complexation of heme group with iron. Prussian blue which has been used
as a dye since olden times is a coordination compound of iron.
It has been established that colour of complex compounds is because of d – d transitions. The
electrons are excited from the lower d-orbitals to the higher d-orbitals. Energy from the visible range
is absorbed in these radiations. Rest of the radiations (energy) are transmitted. It is the transmitted
radiations that form the colour of the substance. It is important to remember that the colour of a
substance is not the radiations that are absorbed but the radiations that are transmitted. We know
that visible (white) light consists of different colours like violet, indigo, blue, green, yellow, orange
and red. If one or more of the radiations are absorbed by a substance, the resultant of the rest of the
colours will be the colour displayed by a substance. If a substance does not absorb any colour, it looks
white. If it absorbs all the colours, it looks black.
84
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 85
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86 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
(iv) Spin quantum number, s. This describes the spin orientation of the electron. Since the
electron can spin only in two ways : clockwise and anticlockwise, s can have only two values :
+ 1 2 and 1 2 . The values may also be indicating by arrows pointing up () and down ()
respectively. It determines the spin angular momentum.
The distribution of electrons in different levels in an atom is known as electronic configuration.
The filling of orbitals is governed by the three well known rules.
1. Aufbau principle. Electrons enter the orbitals of lowest energy first and subsequent electrons
are filled in increasing order of energy (1s, 2s, 2p, 3s, 3p, 4s, 3d ...........).
2. Paulis exclusion principle. No two electrons in an atom can have the same value for the
four quantum numbers.
3. Hund’s rule. When several orbitals of the same energy are available (degenerate orbitals),
the electrons tend to remain unpaired as for as possible i.e., the electrons tend to retain parallel spins
as much as possible, on energy consideration.
The electronic configuration of the outershell is generally represented by a box diagram. The
boxes represent orbitals and electrons are indicated by arrows. For example, the s-orbitals are
indicated by a single box, the p-orbitals are indicated by three boxes, one each for the px , py and pz
orbitals.
Similarly the d-orbitals are represented by five boxes, one each for dxy , dyz , dzx , d x2 y 2 and
d as shown below :
z2
One s-orbtials
Three p-orbitals px py pz
Five d-orbitals d xy d yz d zx d d
x2 y2 z2
The f-orbitals are represented by seven boxes. A spin quantum number of 1 2 is indicated by
the arrow and 1 2 by the arrow . When only one electron is present in a degenerate energy level
such as s, p or d subshell, it can occupy any one of the possible arrangements.
However, for atoms with more than one electron in degenerate orbitals, several different
arrangements are possible which may not have same energy. For example, carbon has the electronic
configuration as :
1s2 2s2 2p2
It has two electrons in 2p subshell. There are 15 different arrangements in which the two
electrons can be added to a set of degenerate three p-orbitals having l = + 1, 0, – 1 corresponding
to px, py and pz
l= +1 0 –1 + 1 0 –1 +1 0 –1 +1 0 –1 +1 0 –1
l= +1 0 –1 +1 0 –1 +1 0 –1 +1 0 –1 +1 0 –1
l= +1 0 –1 +1 0 –1 +1 0 –1 +1 0 –1 +1 0 –1
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 87
Some of these arrangements would be of higher energy and some would be degenerate because
of different inter electronic-repulsions. The inter-electronic repulsions for the arrangement where two
electrons are present in the same orbital are higher than for those arrangements in which they are
present in different orbitals. Consequently, the energy for the former arrangements would be larger
than for those for the latter arrangements. Thus, unlike in a single electron system, many more energy
states exist in multielectron systems. These different arrangements may be grouped into different sets
of degenerate energy states. Furthermore, spin angular momentum (s) and orbital angular momentum
(l) of the electrons may interact or couple to give a resultant angular momentum for the entire multi-
electron atom. The resultant angular momentum and the energy of the system is expressed in a term
symbol. Thus,
term symbols are used to indicate the electronic configuration and the resultant angular
momentum of an atom.
The term symbol for a particular atomic state is expressed as :
2S + 1
LJ
where S = total spin angular quantum number
L = total orbital angular quantum number
J = total angular momentum quantum number
(2S + 1) is called the spin multiplicity of the state (arrangement)
Just as we have the symbols s, p, d, f ........... for l = 0, 1, 2 , 3 ..........., the different values of
L are designated by S, P, D, F, G, H, I, etc. Thus the state S represents L = 0, P represents L = 1 and
so on
L 0 1 2 3 4 5 6 7
State S P D F G H I K
It may be noted that we don’t assign the state J because this letter is used to represent another
quantum number viz. total angular momentum quantum number.
The total angular momentum, J of an atom can be generally determined by two methods. These
are :
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88 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
It is clear from above that the spin multiplicity (2S + 1) is always one more than the
number of unpaired electrons.
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 89
C. Spin-orbital or L – S Coupling
The magnetic effects of the resultant angular momentum, L and the resultant spin moment S
couple together to give new quantum number J called the total angular quantum number. J values
can be obtained by the vectorial combination of L and S by the coupling scheme called Russell
Saunders or LS coupling. The J can acquire all quantized positive values in the range | L – S | to
| L + S | as :
J = (L + S), (L + S – 1), (L + S – 2) .......... | L – S |
The J values are separated by 1. The modulus sign | | indicates the absolute value of | L – S |
so that J 0.
The J value is written as a subscript in the term symbol.
We shall illustrate these rules by taking the examples of p2 and d2 configurations :
p2–Configuration
Step 1
For the two p-electrons l1 = 1 and l2 = 1
L = (1 + 1), (1 + 1 – 1), (1 + 1 – 2)
= 2, 1, 0
States D, P, S
It may be noted that the last value of L can also be obtained by | l1 – l2 | i.e.
1–1=0
The energy states are S, P and D.
Step 2
For two electrons,
1 1 1 1
S = ( 2
2
), ( 2
2
– 1),
= 1, 0
1 1
It may be noted that the second value of S can also be obtained by | s1 – s2 | or 2 2
=0
The spin multiplicity (2S + 1) is :
For S = 1, spin multiplicity = 3 (Triplet)
For S = 0, spin multiplicity = 1 (Singlet)
Therefore, we have six states corresponding to states D, P and S and corresponding to spin
multiplicity 3 and 1 each which can be written as
3S, 3P, 3D, 1S, 1P and 1D.
Step 3
Calculation of J values;
(a) When L = 2, 1 and 0 and S = 1
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 91
In the ground state configuration of carbon, both the p electrons have the same value of n and
l, (n = 2 and l = 1), so they must differ in at least one of the remaining quantum numbers m or s.
Pauli’s exclusion principle restricts the number of terms from 1S, 1P, 1D, 3S, 3P, 3D to 1S, 3P and
1D only. Table 4.1 gives all the fifteen allowed values of M and M for the p2 configuration (which
L S
do not violate Pauli’s principle). It can be shown that these 15 arrangements can be represented by
only three terms 1S, 3P and 1D by taking suitable values of ML (2L + 1) and MS (2S + 1) as illustrated
below :
For p electrons, the angular quantum number l = 1 and magnetic quantum number m has values
from + l ............ 0 ............ – l, giving in this case values of m = 1, 0 , – 1. The spin quantum number
has values of 1 2 and 1 2 for each value of m. The total spin quantum numbers and total orbital
quantum numbers can be obtained by adding the appropriate values of m and l as explained earlier :
ML has values from + L ............ 0 ............ – L (a total of 2L + 1 values).
MS has values from + S ............ 0 ............ – S (a total of 2S + 1 values).
The L and S quantum numbers which are associated with each electronic configuration or term
symbol can be obtained from ML and MS quantum numbers as shown in Table 4.1. The values of
MS and ML can be obtained by adding the appropriate values of ms and n
MS = ms and ML = m
Table 4.1. Allowed values of ML and MS for p2 configuration
S.No. m=+1 0 –1 MS ML Term
ms ml symbol
1D
1. 0 2
2. 0 –2 1D
3. 0 0
3P, 1D, 1S
4. 0 0
5. 0 0
6. 0 1
3P, 1D
7. 0 1
8. 0 – 1
3P, 1D
9. 0 – 1
10. 1 1 3P
11. 1 0 3P
12. 1 –1 3P
13. –1 1 3P
14. –1 0 3P
15. –1 –1 3P
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92 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 93
However, these arrangements can be represented by only five states; 1S, 3P, 1D, 3F and 1G. This
can be seen in a similar way as for p2 electrons.
(i) Maximum value of MS = 1 and the maximum value of ML corresponding to this MS is 3
(Refer to S.No. 2 in Table 4.2). Since this corresponds to L = 3, it represents F state. This occurs
with MS = + 1, 0, – 1 suggesting a triplet F state i.e. 3F.
Now there are 21 combinations of ML and MS values associated with 3F term for L = 3 as
shown below :
ML = + 3 MS = + 1, 0, – 1
ML = + 2 MS = + 1, 0, – 1
ML = + 1 MS = + 1, 0, – 1
ML = 0 MS = + 1, 0, – 1
ML = – 1 MS = + 1, 0, – 1
ML = – 2 MS = + 1, 0, – 1
ML = – 3 MS = + 1, 0, – 1
(ii) The next highest unassigned MS is 0. The corresponding value of ML is 4 (Sr. No. 1 in the
Table 4.2). This corresponds to G state. Since MS = 0, S must be 0 and it is a singlet G term, 1G.
Now, if L = 4, ML can have the values + 4, + 3, + 2, + 1, 0, – 1, – 2, – 3, – 4. If S = 0, MS =
0 (only one value).
Thus, there are nine configurations associated with this term, 1G.
(iii) For ML value of 2, maximum value of MS = 0. This ML = 2 corresponds to D state. Since
MS = 0 for this state, it corresponds to spin multiplicity of 1 suggesting the state 1D.
Table 4.2. Allowed values of MS and ML for the d2 configuration
S.No. m = +2 +1 0 –1 –2 MS = ms ML = ml Term symbol
1. 0 4 1G
2. 1 3 3F
3. 0 3
1G, 3P
4. 0 3
5. –1 3 3F
6. 1 2 3F
7. 0 2
1G, 3F, 1D
8. 0 2
9. 0 2
10. –1 2 3F
11. 1 1
3F, 3P
12. 1 1
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94 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
13. –1 1
3F, 3P
14. –1 1
15. 0 1
16. 0 1
17. 0 1 1G, 3F, 1D, 3P
18. 0 1
19. 1 0
3F, 3P
20. 1 0
21. 0 0
22. 0 0
1G, 3F, 1D, 3P, 1S
23. 0 0
24. 0 0
25. 0 0
26. –1 0
3F, 3P
27. –1 0
28. 0 – 1
29. 0 – 1
30. 0 – 1 1G, 3F, 1D, 3P
31. 0 – 1
32. 1 – 1
3F, 3P
33. 1 – 1
34. –1 –1
3F, 3P
35. –1 – 1
36. 1 –2 3F
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 95
37. 0 – 2
38. 0 – 2 1G, 3F, 1D
39. 0 – 2
40. –1 –2 3F
41. 1 –3 3F
42. 0 – 3
1G, 3F
43. 0 – 3
44. –1 –3 3F
45. 0 –4 1G
Now, if L = 2, ML may have values + 2, + 1, 0, – 1 , – 2
and if S = 0, MS may have (only one value) that is 0.
We can assign this state to five of the combinations (Table 4.2).
(iv) We have some combinations, in which maximum MS = 1 and the maximum ML value
associated with it is 1. Therefore, it corresponds to a P state. Since S = 1, spin multiplicity is 2 × 1
+ 1 = 3. So it corresponds to a triplet P state, 3P.
Now, if L = 1, ML may have values + 1, 0, – 1 if S = 1, MS may have the values + 1, 0, – 1.
Thus, there are nine combinations of ML and MS values :
ML = + 1 MS = + 1, 0, – 1
ML = 0 MS = + 1, 0, – 1
ML = – 1 MS = + 1, 0, – 1
These 9 combinations can thus be assigned the state 3P.
(v) We have considered 21 + 9 + 5 + 9 = 44 combinations so far and only one combination is
left. Combination of MS = 0 and ML = 0 is left. Here L = 0 and it corresponds to singlet. The term
(state) 1S can be assigned to it.
Since L = 0 and S = 0, it corresponds to only one term.
Thus, all the allowed values of ML and MS for d2 configuration may be represented by
1S, 3P, 1D, 3F and 1G states.
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96 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
p2 configuration
The terms for ground state of p2 configuration are 3P, 1D and 1S. We have to find out the ground
state out of these. The most stable state out of these three states is 3P because its multiplicity is
maximum. So, 3P is the ground state (most stable state).
Out of 1D and 1S (both having the same value of S), 1D is more stable because it has a higher
value of L = 2.
No the triplet P state has three terms 3P2, 3P1 and 3P0. According to third rule, 3P0 is the lowest
energy term (because 2p2 configuration of carbon is less than half filled) and these terms may be
arranged in increasing order of energy as
3P < 3P < 3P
0 1 2
The different terms of carbon are arranged in the increasing order of energy in Fig. 4.1. This
order corresponds to experimentally measured energies shown in brackets.
1 1
S S0 –1
(259.0 kJ mol )
1 1
D D2 –1
(122.0 kJ mol )
ENERGY
Carbon
1s2, 2s2, 2p2
(Ground state) 3 –1
P2 (0.52 kJ mol )
3
P 3 –1
3 P1 (0.20 kJ mol )
P
0 3
P0 (0)
Fig. 4.1. Splitting of terms in ground state of carbon
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 97
d2 configuration
The terms for ground state of d2 configuration (e.g. of V3+ ion) as derived earlier are 1S, 3P,
1D, 3F and 1G.
Let us arrange them in increasing order of energy and determine the ground state.
According to rule 1, the stable state corresponds to highest multiplicity. In this case both 3P
and F have common multiplicity 3 (or S = 1). Applying rule 2, 3F term wil be more stable because
3
it has higher value of L i.e. 3 (3P state has L = 1). So energies of these two states are arranged as
3F < 3P.
The remaining three states have same spin multiplicity = 1 (i.e. S = 0). These can be arranged
according to L values as :
1G < 1D < 1S.
The splitting of terms in ground state of d2 configuration are shown in Fig. 4.2. It may be noted
that the two triplet states 3F (3F2, 3F3, 3F4) and 3P (3P0, 3P1, 3P2) can further split and arranged
according to the rule 3 as shown in Fig. 4.2.
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98 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
p1, p5 2P
p2, p4 3P 1S, 1D
p3 4S 2D, 2P
p6 1S
d1, d9 2D
d4, d6 5D 3H, 3G, 3F, 3D, 3P, 1I, 1G, 1F, 1D, 1S
d10 1S
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 99
These microstates differ from one another slightly in energy. The number of microstates may
be calculated from the number of orbitals and the number of electrons using the formula :
n n!
=
r r ! (n r )!
where n is twice the number of orbitals and r is the number of electrons. n! and r! are factorial
n and factorial r respectively.
For a p2 configuration, there are three orbitals, so n = 6 and r = 2.
n 6! 6 5 4 3 2 1
No. of microstates, = = 15 microstates
r
2! (6 2)! 2 1 4 3 2 1
Similarly, for a p3 configuration,
n = 6, r = 3
Using the above relation
n 6! 6 5 4 3 2 1
No. of microstates, = = 20 microstates
r 3! 3! 3 2 1 3 2 1
For a d2 configuration, there are five orbitals so n = 10 and r = 2.
10 10! 10 9 8 7 6 5 4 3 2 1
No. of microstate = = 45 microstates
2 2!8! 2 1 8 7 6 5 4 3 2 1
Using the above formula, the number of microstates for all the electronic arrangements p1 to
p and d1 to d10 can be calculated. These are given in Table 4.5.
6
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100 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
Selection Rules
The main selection rules for electronic spectra are :
1. Transitions in which there is change in the number of unpaired electrons in going from a
lower to a higher energy state are referred to as spin or multiplicity forbidden. This means that
transitions to only those excited states are to considered which have the same spin multiplicity as
the ground state. This is also known as S = 0 rule.
For example, for a d2 configuration, we observe transitions from 3F (ground state) to 3P (excited
state) because both 3F and 3P terms have same spin multiplicity 3. The transitions in which S 0(e.g.
S = ± 1) are forbidden or very very weak.
2. For molecules having a centre of symmetry, transitions which do not involve a change in
the subsidiary quantum number (l = 0) are forbidden. These forbidden transitions are called
Laporte forbidden transitions.
We can say that the transitions which involve a change in the subsidiary quantum number i.e.
l = ± 1 are Laporte allowed transitions and have a high absorbance. This rule suggests that
transitions from one d-level to another d-level (i.e. d–d transitions) in transition metal complexes are
not allowed (Laporte forbidden transitions) because l = 0.
This would suggest that transition metal complexes should not give d–d transitions and should
not give colours. But, actually it is not so. The transition do take place with the help of slight
relaxation in Laporte rule as explained below :
(i) If the transition metal complex ion does not have perfect octahedral structure, but is slightly
distorted so that the centre of symmetry is destroyed, then mixing of d and p-orbitals of the metal
ion may occur. In such a case, the transitions are no more pure d-d transitions but they occur between
d-levels with varying amounts of p-character. The intensity of such transitions is very weak in the
range = 20 to 50. Thus, octahedral complexes in which all the ligands are not same such as
[Co(NH3)5 Cl]2+ have irregular octahedral structure and do not possess a centre of symmetry. d–d
transitions with varying amounts of p-character take place giving this compound a colour.
The tetrahedral complexes such as [MnCl4]2–, [MnBr4]2– etc. also do not possess a centre of
symmetry because a tetrahedron shape never possesses a centre of symmetry. Thus, intense transitions
are observed in these complexes which result in their deep colours. However, mixing of d and p
orbitals does not occur in perfectly octahedral complexes, which have a centre of symmetry such as
[Co(NH3)6]3+.
(ii) A complex which has a perfect octahedral structure can also exhibit absorption spectrum
because the bonds in the transition metal complexes are not rigid but undergo vibrations that may
temporarily change the centre of symmetry. These vibrations continue all the time and at any
particular time some ligands may spend an appreciable amount of time out of the centro symmetric
equilibrium position. As a result, the molecule may possess distorted octahedral symmetry so that
small amount of mixing of d and p-orbitals occurs and therefore, low intensity ( = 5 to 25) spectra
are observed. These transitions are called vibronically allowed transitions and the effect is called
vibronic coupling. For example, in [Mn(H2O)6]2+ complexes, all transitions are spin multiplicity
forbidden and Laporte forbidden. But the complex ion is pale pink in colour. This is explained by
vibronic coupling which results in very low intensity transitions.
In short Laporte allowed transitions are very intense while Laporte forbidden transitions vary
from weak intensity, if the complex is non centro symmetric to very weak if it is centro symmetric.
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 101
A2g
12Dq
Increasing Energy
T2g
Eg
2Dq
F
6Dq
D
6Dq
4Dq
T 2g T1g
(a ) (b)
Fig. 4.3. Splitting of spectroscopic terms arsing from
(a) d electronic arrangement and (b) f 1 electronic arrangement
1
Robert S. Mulliken
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102 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
If may be noted that common Mulliken symbols are used in the octahedral and tetrahedral field
these are distinguished by introducing the symmetry symbol ‘g’ in octahedral field (Table 4.6)
Table 4.6. Correlation of Spectroscopic terms into Mulliken symbol
Spectroscopic Mulliken Symbol
Term Octahedral field Tetrahedral field
S A1g A1
P T 1g T1
D Eg + T2g E + T2
F A2g + T1g + T2g A2 + T1 + T2
G A1g + Eg + T1g + T2g A1 + E + T1 + T2
We can obtain Mulliken symbols if we know the spectroscopic terms S, P, D, F, etc. It may be
recalled that
(i) The term S stands for resultant angular momentum L, when L = 0. The number of
components of L is 2L + 1. When L = 0, this is called one component term and is represented
by A.
(ii) The term P means L = 1 which has 3 components (2L + 1). It is triply degenerate and is
represented by T.
(iii) The term D means L = 2 which has 5 components (2L + 1). This is constituted of doubly
degenerate E and a triply degenerate T terms.
(iv) The term G means L = 3 which has 7 components (2L + 1). This is constituted of one singly
degenerate A, a doubly degenerate E and two triply degenerate T1 and T2 terms.
We observe from the Table 4.6, that the singly degenerate term is sometimes represented by
A1 and sometimes by A2. Similarly triply degenerate terms are represented by T1 or T2. The numbers
1 and 2 define symmetry to Mulliken symbols and are derived from group theory.
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 103
With ligands having vacant * or d-orbitals, there is possibility of -back bonding with the
ligands. Such ligands are called -acceptors. This interaction to bonding scheme increases . The
ligands which can do this effectively are CN–, CO, etc. With -donor strength, ligands can be arranged
in terms of their donor atoms as :
halogen < oxygen < nitrogen < carbon
The metal ion also influences although not to the extent of ligands the magnitude of 0 through
the overlap and energy match criteria. The following metal ion spectrochemical series is observed.
Mn2+ < Ni2+ < Co2+ < Fe2+ < Fe3+ < Cr3+ < Co3+ < Mn4+ < Mo3+ < Pd4+ < Ir3+ < Re4+ < Pt4+
The crystal field splitting is influenced by the oxidation state of transition metal ion. Higher
the oxidation state of metal ion greater is the crystal field splitting.
0.6 0 or 6 Dq
Molar absorbance
Average energy
Energy
5
level
0.4 0 or 4 Dq
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104 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
The ground state terms for a free ion with d1 configuration is 2D and it is shown on the left
(Fig. 4.5). Under the influence of a ligand field, this splits into two states which are described by
Mulliken symbols 2Eg and 2T2g. The lower T2g state corresponds to the single d-electron occupying
one of the T2g orbitals and 2Eg state corresponds to the electron occupying one of the Eg orbitals.
The two states 2Eg and 2T2g are separated more widely as the strength of the ligand field increases.
2
Eg
6 Dq
Energy 2 Bary centre
D
4 Dq
2
T2g
4 Dq
Energy
2
D Bary centre
6 Dq
2
Eg
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 105
2
Eg 1 9 2
T2g
d (Oh) d (Oh)
6 Dq
0 Bary
Energy
2
D centre
4 Dq
2 2
T2g Eg
O
Increasing (Dq) Increasing (Dq) Leslie Orgel
Fig. 4.7 Splitting of energy levels for d1 and d9 configurations in an octahedral field (Oh)
2
D
2 2
T E
O
Increasing (Dq) Increasing (Dq)
Fig. 4.8. Splitting of energy levels for d1 and d9 configurations in a tetrahedral field (Td)
To summarise, we can say
d1 (Td) is inverse of d9 (Td) as well as d1 (Oh)
d9 (Td) is inverse of d1 (Td) as well as d9 (Oh)
We can check that the value of L is the same in the case of d1 and d6 configurations, but the
spin multiplicities are different
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106 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
+2 +1 0 –1 –2
1 1
d L = 2, spin multiplicity (2S+1) = (2× + 1) = 2
2
6
d L = 2, spin multiplicity (2S+1) = (2 × 2 +1) = 5
Thus the term symbols for d1 and d2 configurations are 2D and 5D respectively. The state D
splits into doubly degenerated term E and triply degenerate tem T in octahedral as well as tetrahedral
fields. Consequently, only a single d-d transition can occur. Thus, we come to know that electronic
transitions will be similar for d9 (2D) and d4 (5D). In other words, transitions in metal ions differing
by five d-electrons in their configurations give similar transitions in octahedral and tetrahedral fields.
From the Orgel diagram (Fig. 4.9) it is apparent that d1, d4, d6 and d9 ions should also give
only one d-d absorption band. Splitting of the states as a function of o for octahedral complexes
with d1 and d6 electron configurations and tetrahedral complexes with d4 and d9 electron
configurations are described on the left handside. The spectra of these complexes contain only one
band arising from d-d transitions and is assigned as T2g Eg.
The right hand side of the Orgel diagram applies to octahedral complexes with d4 and d9
electron configurations and tetrahedral complexes with d1 and d6 electron configurations. The
spectra of these complexes contain only one band arising from single d-d transitions and is assigned
as E T2. For tetrahedral complexes we drop the subscripts because a tetrahedron does not
have centre of symmetry.
Eg 1 6 4 9 T2g
d ,d (Oh) d ,d (Oh)
4 9 1 6
d ,d (Td) d ,d (Td)
T2g Eg
O
Increasing (Dq) Increasing (Dq)
Fig. 4.9. Orgel diagram of d1, d4, d6 and d9 complexes in octahedral and tetrahedral fields
From the Orgel diagram (Fig. 4.9), we conclude that electronic transitions in:
d1 (Oh) = d6(Oh) but inverse of d9 (Oh) = d4 (Oh) and
d1(Td) = d6 (Td) but inverse of d9(Td) = d4 (Td)
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 107
3F
is the ground state with lowest energy and 3P, 1G, 1D and 1S are excited states in accordance
with Hund’s rule. The transitions from the level 3F are allowed to another triplet state i.e. 3P. The
transitions from 3F to 1S, 1D and 1G states are spin forbidden and are not observed. p-orbitals are
not split in an octahedral field and so P states are not split but are transformed into a3 T1g state while
the f-orbitals are split into three levels and so 3F state splits into 3A2g + 3Tlg + 3T2g. The energy
level diagram for these is shown in Fig. 4.10 (a).
3
A2g (F)
3 3
T1g (F) T1g (P)
3 3
T1g (F) A2g
3
T1g (P) 10
Molar absorbance
3
3
T2g (F)
3 3
P T1g (F) T2g
Energy
3
F 5
Fig. 4.10 (a) Transitions for V3+ (d2) ion and (b) Absorption spectrum of a d2 complex [V(H2 O)6]3+.
We expect three peaks corresponding to three transitions as shown in Fig. 4.10 (a). The three
transitions are from the ground state 3T1g (F) to 3T2g 3T1g (P) and 3A2g respectively. The spectrum
of [V(H2O)6]3+ is shown in Fig. 4.10 (b) which shows only two peaks. The peak at ~17,000 cm–1
is assigned to 3Tlg (F) 3T2g (F) and the peak at 24,000cm–1 is due to both 3T1g (F)
3T (P) and 3T (F) 3A
1g 1g 2g transitions.
2+
Thus, for [V(H2O)6] , the bands are assigned as:
3T (F) 3T2g (F) 17,000 cm–1
1g
3T (F) 3A2g (F) 24,000 cm–1
1g
The energies corresponding to these two transitions lie very close to each other and therefore,
these two transitions are not resolved into two separate peaks.
However, with strong field ligands like NH3, we get three bonds which may be assigned as:
3T (F) 3T2g (F) 17,200 cm–1
1g
3T (F) 3T 1g (P) 25,600 cm–1
1g
3T (F) 3A2g (P) 36,000 cm–1
1g
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108 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
The transition 3A2 (F) 3T2 (F) is of very low energy and does not fall in the visible
region and hence is not observed in the electronic spectrum of d2 (Td).
(c) d8 Octahedral
The complexes of metal with d8 configuration can be treated similar to d2 octahedral
complexes. There are two holes in the eg level and therefore, promoting one electron is equivalent
to transferring a hole from eg to t2g level. This is inverse of d2 case and is shown in Fig. 4.11. As
explained earlier 3P state is not split and is not inverted but the 3F state is split into three states and
is inverted. Hence the ground state term for Ni2+ is 3A2g. It may be noted that in both d2 and d8
configuration, the 3F state is the lowest energy state. Three spin allowed transitions are observed
in spectra of [Ni (H2O6]2+, [Ni (NH3)6]2+, etc. The transitions correspond to the following.
3A 3
2g T2g (F)
3T 3
2g A1g (F)
3TA 3
2g A1g (P)
3
3 T1g (P)
P
3
T1g (F)
Energy
3
3
F T2g
3
A2g
Ligand field strength
Fig. 4.11 Energy level diagram for d8 ion.
It may be noted that d2 octahedral energy level diagram is similar to the high spin d7
octahedral and d3 and d8 tetrahedral cases. The inverse diagram is similar for d3 and d8 octahedral
and d2 and d7 tetrahedral complexes.
Fig. 4.12 gives Orgel diagram for two electrons and two hole configuration 4.12. In this figure,
the two T1g states, one from P state and other from F state are slightly curved lines. This may be
attributed to mixing between the two T1g terms arising from the high energy P term and low energy
F term because of same symmetry possessed by them.
3
8 Energy 2 A2g (F)
3 d (Oh) d (Oh ) 3
T1g (P) 2
d (Td ) 3
8
d (Td) T1g (P)
P
3
T1g (F)
3 3
F T2g (F)
3
T2g (F)
3
T1g (F)
3
A2g (F)
O Dq
Increasing ligand field Increasing ligand field
Fig. 4.12. Orgel diagram for two electron (d2) and two hole (d8) configuration
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 109
4
F
4
T2g(F)
4
A2g
Ligand strength
Fig. 4.13 Energy level diagram for a d3 ion.
The Orgel energy level diagram is shown in Fig. 4.13. The spectra of Cr (III) complexes would
be expected to show three absorption peaks corresponding to the following transitions:
For [Cr(H2O)6]3+
4A (F) 4T2g (F) 17,400 cm–1
2g
Complex
4A 4
2g T1g (F) 22,700 24,700 23,000 28,500 32,200
4A 4
2g T1g (P) 34,400 38,600 –– –– ––
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110 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
0.03 4
A1g
Molar absorbance
4 4G
Eg
4
0.02 4 T2g (4D)
T1g (4G)
4
T2g (4G) 4
Eg (4D)
0.01
D 4
30000 Eg
4
4 4 T2g
P E g 4A
4 1g
G 4
20000 T2g
4
T1g
10000
6
6 A1g
S
500 1000
Ligand field strength
Fig. 4.15. Orgel energy level diagram for Mn2+ (d5) octahedral
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 111
multiplicity compared to the ground state and therefore, transition to these excited states are spin
multiplicity forbidden. However, due to weak spin orbital interactions, these types of transitions
are not totally forbidden but give rise to weak absorption bands.
(b) For the ground state term 6S, there are 11 excited states (4G, 4F, 4D, 4P, 2I, 2H, 2G, 2F,
2D, 2P, 2S. Out of these 11 excited states only four quarters, 4G, 4F, 4D and 4F involve the reversal
of only one spin. Rest of the seven states are doublets and are doubly spin forbidden and are unlikely
to be observed. In octahedral field, these four states split into ten states and therefore, upto ten weak
absorption bands may be observed as shown in Fig. 4.15.
(c) Calculations shows that width of the peaks for d-d transitions vary directly as the slope
of the higher energy state relative to the slope of the ground state in the Orgel diagram. Fig. 4.15
shows that the ground state 6S does not split but transforms to 6A1g state which is drawn along the
horizontal line. The 4Eg(G), 4A1g (G), 4Eg(D) and 4A2g(F) terms are also horizontal lines. So, their
energies are independent of the crystal fields. Since the slope of the ground state terms 6A1g is zero
and the slopes of 4Eg(G), 4A1g(G), 4Eg(D) and 4A2g (F) terms are also zero, transitions from the
ground state to these four states should give sharp peaks. Similarly, the peaks due to transitions to
4T (G) and 4T (G) will give broad peaks. These bands are listed as under.
1g 2g
6A 4T 1g 18900 cm–1
1g
6A 4T2g (G) 23100 cm–1
1g
6A 4E g
1g 24970 and 25300 cm–1
6A
1g
4A1g
6A 4T2g (D) 28000 cm–1
1g
6A 4Eg (D) 29700 cm–1
1g
For tetrahedral complexes of d5 electronic configuration, the same diagram is applicable.
3. Cobalt (III) octahedral complex ions : d7 (Oh)
In octahedral field of weak ligands, Co(II) has the electronic configuration as : t2g5 eg2. Thus
it has three unpaired electrons. The ground state term is 4F which is transformed to 4T1g (F), 4T2g
and 4A2g. The other quartet states is 4F which does not split but transforms into 4T1g(P) state is an
octahedral field. The energy level diagram is shown in Fig. 4.16.
4
A2g
4
T1g(P)
4
P
Energy
4
T2g
4
F
4
T1g(F)
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112 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
Molar absorbance
4
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 113
600
400
Molar absorbance
200
3A
(F) 3T1g (P) 26,000 cm–1
2g
Similarly, these band in [Ni(NH3)6]2+ complex ocur at 10800, 17500 and 28200 cm –1
respectively. The bands are quite weak as expected.
10
Molar absorbance
3 3
5 A2g T1g(P)
3 3
3 3 A2g T2g
A2g T1g(F)
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114 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
ml
+1 0 –1
ms:
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 115
Example 2. The [Ti (H2O)6]3+ complex absorbs at 5000Å. Calculate 0 for this absorption.
N 0hc
Solution. E = N0 hv =
For [Ti (H2O)6]3+
= 5000Å = 5000 × 10–10 m, c = 3.0 × 108 ms–1, h = 6.626 × 10–34 Js
N0 = 6.023 × 1023. Substituting the values in the equation above
6.023 10 23 6.626 10 –34 3.0 108
E = =239 kJ mol–1
5000 10 –10
0 for the complex = 239 kJ mol–1.
Example 3. Derive the term symbols for d10 configuration.
Solution. In a d10 configuration
2 1 0 –1 – 2
ML= 0 so L = 0 and it corresponds to ‘S’ state.
Ms= 0 and so S = 0 and therefore, multiplicity is 2S + 1 = 1
Term symbol : 1S
It may be noted that for a closed configuration, the term symbol is always 1S.
Example 4. The tetrahedral complexes of Mn (II) are more intensely coloured than the
octahedral complexes of Mn (II). Explain.
Solution. Manganese (II) has d5 electronic configuration. Tetrahedral Mn (II) complexes are
yellow green. The d–d transitions in tetrahedral Mn (II) complexes are quite intense than octahedral
complexes. These d–d transitions are Laporte allowed because tetrahedral molecules do not possess
centre of symmetry. The transitions in Mn (II) d5 are also multiplicity allowed due to mixing of d-
and p-orbitals in tetrahedral geometry. Hence we observe intense coloured Mn (II) tetrahedral
complexes.
On the otherhand, in [Mn (H2O)6]2+ octahedral complexes, the transitions are both Laporte
forbidden (due to centre of symmetry) and multiplicity forbidden because ground term 6A1g is the
only term with multiplicity 6 and all other terms are of lower multiplicity. Therefore, the bands are
very weak.
Example 5. Identify the ground state terms from each set of terms:
(i) 1S, 3P, 1D, 3F, 1G
(ii) 1S, 3P, 1D
(iii) 1S, 2P, 2D, 3F, 1G
Solution. (i) 3F because although it has same multiplicity as 3P but it has higher value of L
(=3) and hence more stable.
(ii) 3P because it has highest multiplicity.
(iii) 3F because it has highest multiplicity.
Example 6. Calculate the number of microstates for:
(i) d1 (ii) p3 (iii) d4 configurations
Solution. (i) d1
Here n = 10, r = 1
Applying the formula to calculate number of microstates
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116 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
10 9 8 7 6 5 4 3 2 1
= = 10
1 9 8 7 6 5 4 3 2 1
(ii) p3
n = 6, r=3
6! 6! 6 5 4 3 2 1
No. of microstates = 3!(6 – 3)! = = = 20
3!3! 3 2 1 3 2 1
(iii) d4
n = 10, r=4
10! 10! 10 9 8 7 6 5 4 3 2 1
No. of microstates = 4!(10 – 4)! = = = 210
4!6! 4 3 2 1 6 5 4 3 2 1
Example 7. Determine the term symbol for ground state of nitrogen.
Solution. The electronic configuration of nitrogen, N is 1s2 2s2 2p3. We consider only 2p
subshell because the inner orbitals are filled.
l + 1 0 –1
2p
ML = +1 + 0 – 1 = 0 It corresponds to state S.
1 1 1 3
MS =
2 2 2 2
23
Spin multiplicity 2S + 1 = 1 = 4
2
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 117
ML = + 1 + 0 = 1 State = P
1 1
MS = + =1 S=1
2 2
Spin multiplicity, = 2S + 1
= 2 × 1 + 1= 3
Term symbol : 3P
(ii) d1s1
2 1 0 – 1 – 2 0
ML = 2 + 0 = 2 State = D
1 1
MS = + =1 S=1
2 2
Spin multiplicity, = 2S + 1 = 2 × 1 + 1= 3
Term symbol : 3D
(iii) d7s1
2 1 0 – 1 – 2 0
ML = 4 + 2 + 0 – 1 – 2 + 0 = 3 State = F
1
MS = 4 × =2 S = 2
2
Spin multiplicity, 2S + 1 = 2 × 2 + 1 = 5
Term symbol : 5F
Example 10. What terms arise from p1d1 configuration?
Solution.
1 0 –1 2 1 0 – 1 – 2
p
For a p1d1 configuration,
ML = +1 + 2 = 3 Term = F
The electrons may be paired, S = 0 or parallel, S = 1
Spin multiplicity 2S + 1 = 2 × 0 + 1 = 1 or 2 × 1 + 1 = 3
Terms 1F and 3F are possible corresponding to the two spin multiplicities
Example 11. Calculate the number of microstate for
(i) p4 and (ii) d4 configurations.
Solution. Microstates can be calculated using the formula :
n n!
No. of microstates : =
r r ! (n r )!
n = twice the no. of orbitals and r = the number of electrons.
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118 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
(i) for p4
n = 6, r = 4, Substituting the values
6!
No. of microstates =
4! (6 4)!
6! 6 5 4 3 2 1
=
4! 2! 4 3 2 1 2 1
= 15 microstates
(ii) for d4 configuration,
n = 10, r = 4, Substituting the values, we have
10! 10!
No. of microstates =
4! (10 4)! 4! 6!
10 9 8 7 6 5 4 3 2 1
=
4 3 2 1 6 5 4 3 2 1
= 210 microstates
Example 12. What is vibronic coupling? Give one example of this phenomena.
Solution. The d-d transition in octahedral complexes are Laporte forbidden on symmetry
consideration. However an octahedral (Oh) complex may absorb light in the following manner.
The bonds in the transition metal complexes are not rigid but may undergo vibrations that may
temporarily change the symmetry. Some of the molecules may slightly be distorted from octahedral
symmetry at a given time. For example, octahedral complexes vibrate in a way in which the centre
of symmetry is temporarily lost. This phenomenon is called vibronic coupling. As a result, d-d
transitions having molar absorptivities in the range of approximately 10 to 50 L mol–1 cm–1 are
commonly observed. These are also responsible for the bright colour of many of these complexes.
For example, this phenomenon is observed in [Mn(H2O)6]2+. In this case, the transitions are both
multiplicity and Laporte forbidden. The complex is coloured. Had there been no vibronic coupling
it would have been colourless. These transitions are vibronically allowed and the effect is called
vibronic coupling.
Example 13. Calculate the term symbols for ground state of
(i) Cr (3d5 4s1) and (ii) Ni (3d8 4s2).
5
Solution. (i) Cr : 3d 4s 1
2 1 0 –1 – 2 0
3d 4s
ML = + 2 + 1 + 0 – 1 – 2 + 0 = 0 State = F
1
MS = + × 6 = 3, S =3
2
Multiplicity, 2S + 1 = 2 × 3 + 1 = 7
J = 3 (because L = 0)
Term symbol for ground state = 7S3
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 119
Example 16. Determine the ground terms for low spin and high spin d6 octahedral
configurations.
Solution. High spin :
2 1 0 – 1 – 2
ML = + 2 + 2 + 1 + 0 – 1 – 2 = 2 State = D
1
MS = 4+ = 2
2
Spin multiplicity = 2 × 2 + 1 = 5
Term symbol = 5D
Low spin :
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120 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
ML = + 2 + 2 + 1 +1 + 0 + 0 = 6, State = I
MS = 0 Multiplicity = 2 × 0 + 1 = 1
Term = 1I
Example 17. Determine the possible values of J for the term obtained from a d 2
configuration.
Solution. For d2 configuration:
l1 = 2, l2 = 2
L = (2 + 2), (2 + 2 –1), (2 + 2 –2), (2 + 2 –3), (2 + 2 –4)
=4 3 2 1 0
States = G, F, D, P, S
1 1 1 1
Since there are two electrons so, S = 1 2 2 , 0 2 – 2
or Spin multiplicity S = (2S + 1) = 3, 1
Possible values of J are:
L = 4, S = 0, J = 4 1G
L = 3, S = 1, J, 4, 3 3F
L = 2, S = 0, J = 2 1D
L = 1, S = 1, J = 2, 1, 0 3P
L = 0, S = 0, J = 0 1S
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 121
Total 20
EXERCISES
(Including Questions from Different University Papers)
Multiple Choice Questions (Choose the correct option)
1. Ground state term symbol for He (1s2) is
(a) 1S1/2 (b) 1S0
(c) 0S1/2 (d) none of these
2
2. Ground state term for d configuration is:
(a) 3F (b) 3P (c) 1G (d) 1S
3+
3. The colour of the complex ion, [Ti(H2O)6] is due to:
(a) presence of water molecules
(b) intermolecular vibrations
(c) excitation of electron from t2g to eg energy level
(d) excitation of electron from 3d to 4s energy level
4. The number of microstates for a p2 configuration is
(a) 10 (b) 20 (c) 18 (d) 15
5. For L = 0 and S = 1, full spectroscopic term is :
(a) 3D1 (b) 1S1 (c) 3S1 (d) 1P3
6. Which of the following electronic arrangement has maximum number of microstates?
(a) d 5 (b) d 3 (c) d 6 (d) d 9
5
7. Ground state term of d configuration is :
(a) 6S (b) 4F (c) 2D (d) 3P
8. For Laporte forbidden transitions
(a) l = 0 (b) S = 0 (c) l = –1 (d) l = ±1
9. Mulliken symbol for spectroscopic term P in octahedral field is
(a) A1g (b) T 1g (c) T 2g (d) Eg
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122 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
ANSWERS
1. (b) 2. (a) 3. (c) 4. (d) 5. (c) 6. (a)
7. (a) 8. (a) 9. (b) 10. (c) 11. (a) 12. (a)
13. (b) 14. (d)
General Questions
1. (a) Why do tetrahedral complexes of an element give much more intense d-d spectra than
its octahedral complexes?
(b) Discuss the electronic spectra of [Co(H2O)6]2+ and [CoCl4]2– complexes.
2. (a) Find the ground state term for each of the following configuration:
(i) d 3 (ii) d 5 (iii) d 9
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 123
(b) What are spin multiplicity forbidden and Laporte forbidden transitions?
3. (a) What are selection rules for electronic spectra?
(b) Discuss the spectral features of Mn(II) in octahedral complexes of weak and strong
ligand fields.
(c) Write briefly about L – S coupling.
4. (a) The correlation diagram for a d2 configuration as in V3+ (aq) ion does not give simple
0 value unlike the crystal field splitting diagram. Which transition from the ground state
3T would give value?
1g 0
(b) Define spectroscopic term. Find the terms for atoms with the following configurations:
(i) s1 (ii) s1p1 (iii) p1
(c) Discuss the absorption spectra for Co (II) octahedral and Co (II) tetrahedral complexes.
(d) Discuss the nature of electronic transitions in octahedral complexes of metal ions with
d6 (high spin) configuration.
5. (a) Calculate the ground state terms with spin multiplicity for the following octahedral ions:
V3+, Ni2+, Cu2+.
(b) What is L-S coupling? How does it help to calculate the resultant angular momentum
(J) of an atom having two electrons in a d- subshell.
(c) Draw combined Orgel diagram for d1, d 4, d 6 and d 9 complexes.
6. (a) Discuss the Orgel diagram and absorption spectra for a d 8 ion.
(b) According to Laporte selection rule, electronic transitions of the d-d type displaced in
spectra of octahedral complexes should be forbidden. Why are moderately strong spectra
actually observed?
(c) The absorption spectrum of Ti3+ (aq) (d1) is attributed to a single t2g eg transition.
Explain the position, intensity and broad nature of this band.
7. (a) Determine the ground state term symbol of anion with d1 configuration.
(b) What is meant by spectrochemical series?
(c) Draw combined Orgel diagram for d1, d 4, d 6 and d 9 complexes.
(d) Write briefly about L – S coupling scheme of angular momenta.
8. (a) Identify the ground state term from each set of the following terms:
(i) 1S, 3P, 1D
(ii) 1S, 2P, 2D, 3F, 1G
(iii) 1S, 3P, 1D, 3F, 1G
(b) For [V(H2O)6]3+ two absorption bands are observed at 17,800 and 25,700 cm–1. Assign
these bands.
(c) Explain as to why Co(II) octahedral complexes are light pink while tetrahedral species
are intense blue in colour?
9. (a) Draw the energy level diagram for d2 configuration in tetrahedral and octahedral fields
showing three possible transitions.
(b) How does Hund’s rule help to arrange the different spectroscopic terms in order of their
increasing energies? How does it help to find the term in ground state?
(c) Name the largest energy transition for high spin octahedral complexes for V3+, Ni2+,
Cr3+, and Cu2+.
10. (a) Discuss Russel-Saunders states for d 2 configurations.
(b) Give energy level diagram and electronic spectra of Cr (III) octahedral complexes.
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124 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
11. (a) Discuss the special features of electronic spectra of [Ni(H2O)6]2+ ion.
(b) Draw combined Orgel diagram for d1, d 4, d 6 and d 9 complexes.
12. (a) Write a short note on L-S coupling.
(b) Discuss special features of electronic spectra of Cr (III) octahedral and Mn (II)
octahedral complex ions.
13. (a) Find out the ground state terms with spin multiplicity for Cu2+ and V3+ ions.
(b) Name the factors which govern the magnitude of .
(c) Draw an Orgel diagram for d 3 in Oh complex.
14. (a) Show how one gets the following terms for d 2 configuration:
1G, 3F, 1D, 3P and 1S. Which of these belong to ground state?
(b) Will the electronic spectra of [Co(H2O)6]2+ and [CoCl4]2– be same? If not explain the
differences that one encounters.
(c) Electronic transition of the d-d type displayed in the spectra of octahedral transition metal
complexes should be forbidden by the Laporte selection rule. Why are moderately strong
spectra actually observed? Is this the reason that spectrum of [Co(H2O)6]2+ is less easy
to interpret?
15. (a) Derive Russel-Saunders states for d 2 configuration. Arrange these in accordance with
their increasing energies diagrammatically.
(b) What are Orgel diagrams? Draw and discuss the Orgel energy level diagram for
[Cu(H2O)6]2+ ion.
(c) Discuss in details the electronic spectrum of [Ti(H2O)6]3+ complex ion.
16. (a) What is L-S coupling scheme to derive the energy states of d 2 system?
(b) Discuss special features of electronic spectra of Co(II) octahedral and Co(II) tetrahedral
complex ions.
17. (a) Arrange the different spectroscopic terms of titanium with the help of Hund’s rules.
(b) Discuss the special features of the electronic spectrum of [Co(H2O)6]2+ ion.
(c) State and explain the Laporte selection rule.
18. (a) Why do tetrahedral complexes of an element give much more intense d-d specrta than
its octahedral complexes?
(b) What are the two important limitations of Orgel energy level diagrams?
19. (a) What do you understand by a term symbol? Derive the term symbols for p2-configuration
and calculate the ground state term using Hund’s rule or L-S coupling scheme.
(b) Draw combined Orgel–Energy level diagram for d1 and d 9 octahedral complexes.
20. (a) Define L–S coupling.
(b) What is spectrochemical series.
(c) Why is [Ti(H2O)6]3+ ion violet?
(d) Describe electronic spectra of [Mn(H2O)6]2+.
21. (a) Derive the term symbols for d 2 configuration.
(b) [Ti(H2O)6]3+ is purple in colour. Explain.
(c) Describe the vibronic coupling with example.
22. (a) What are Orgel diagrams? What information is conveyed by these diagrams?
(b) Give a detailed account of the selection rules of electronic spectra.
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ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 125
23. (a) Why do tetrahedral complexes of d-block elements give much more intense d-d spectra
than its Oh complexes?
(b) Derive the ground state term symbol for an atom with the help of L-S coupling for d2
and d6 configuration?
24. (a) Derive the term symbols for p6 and d10 systems.
(b) Draw Orgel diagram for d1 and d 9 systems.
25. (a) Discuss the nature of electronic transitions in d 6 octahedral.
(b) Tetrahedral complexes of Mn(II) are more intensely coloured than the octahedral
complexes of Mn(II) explain.
(c) Draw Orgel diagram for d1 complexes.
26. (a) Draw Orgel diagram for d1 and d9 system.
(b) State any two selection rules for electronic spectrum of transition metal complexes.
Discuss exception if any.
(c) Identify ground term assuming L–S coupling for ions.
(i) 2p2 (ii) 3d 8
27. (a) Find out the ground state term for the following octahedral ions: Cu+2, V+3 and Ni+2.
Write their multiplicity also.
(b) Draw a combined Orgel diagram for d1, d 4, d 6 and d 9 complexes in octahedral and
tetrahedral complexes.
(c) The absorption Ti3+ (aq), d1 is attributed to single (i) t2g eg transition. Explain the
position, intensity and broad nature of the band.
28. (a) The complex [Ti(H2O)6]3+ shows a single absorption band at 20,300 cm–1, Calculate
(Crystal field splitting energy).
(b) What will be the term symbol for ground state for configuration d3.
(c) Draw Orgel diagram for d2 configuration in octahedral complexes.
29. (a) Calculate the term symbol for ground state of Cr.
(b) For [V(H2O)6]3+ two absorption bands are observed at 17780 and 25700 cm–1. Assign
these bands.
(c) State and explain Hunds rule for assigning ground state spectroscopic term with suitable
examples.
30. (a) Find the Russel-Saunders terms for p2 configuration. What will be the ground state?
Draw their splitting diagram in terms of energy.
(b) Why do tetrahedral complexes give much more intense d-d transition than octahedral
complexes?
(c) Find the ground state term for [Ti(H2O)6]3+ ion. Comment upon the colour of this
complex ion.
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