CHAPTER 8

Electronic Spectra of Transition Metal Complexes:

 Spectroscopic Ground States
The spectra of transition metal complexes is not as simple as it appears from just the splitting of d-
orbitals with electrons get promoted from the lower energy orbital set to a higher energy orbital set. Actually,
energy levels of a transition metal atom or ion with a particular electronic configuration are described not only
by the electronic configuration itself but also by different types of electronic interactions such as spin-spin,
orbital-orbital or spin-orbital which can be categorized by some special symbols, called as term symbols. The
ground state term symbol is predicted by Hund's rule. In other words, the term symbol in quantum mechanics
is an abbreviated description of the total angular momentum quantum numbers in a multi-electron atom.
However, the quantum mechanical states of a single electron can also be described by a term symbol.
 Calculation of Microstates in a Particular Electronic Configuration
The various overall-arrangements of electronic cloud around the nucleus for a particular
configuration are not the same as far as the energy and angular momentum are concerned. These different
electronic arrangements can be classified on the basis of overall spin, orbital or total angular momentum.
The term microstates may be defined as the overall electronic arrangements of a particular electronic
configuration which can be differentiated in terms of energy or angular momentum.
The two types of electronic configurations for which the microstate calculation has to be carried out
are discussed below.
1. When unpaired electrons are present in the same subshell:
i) p1-configuration: Let us consider that we want to study the number of ways in which a single electron can
be filled in any p-subshell.

1 ↑

2 ↓

3 ↑

4 ↓

5 ↑

6 ↓

px py pz

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 CHAPTER 8 Electronic Spectra of Transition Metal Complexes: 215

ii) p2-configuration: Let us consider that we want to study the number of ways in which two electrons can be
filled in any p-subshell.

1 ↑ ↑

2 ↑ ↑

3 ↑ ↑

4 ↓ ↓

5 ↓ ↑

6 ↓ ↓

7 ↑ ↓

8 ↑ ↓

9 ↑ ↓

10 ↓ ↑

11 ↓ ↑

12 ↓ ↑

13 ↑↓

14 ↑↓

15 ↑↓

px py pz

Hence, the total number of ways in which one and two electrons can be arranged in the p-subshell of
an atom or ion are six and fifteen, respectively. However, the calculation of the number of microstates for the
configurations like d2 or f2 using the abovementioned method is quite lengthy and difficult. Moreover, as we
are interested only in the number of these electronic arrangements and not in the nature; permutation and
combination can be used to find out all these numbers as follows:

𝑛 𝑛!
No. of microstates = ( ) =
𝑟 𝑟! (𝑛 − 𝑟)!

Where n is twice the number of orbitals present in the subshell under consideration and r is the number of
unpaired electrons in them. The formulation related to the calculation of the number of microstate in particular
term symbol will be discussed later in this chapter.

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Now, the number of microstates for different electronic configurations can be calculated easily.
i) For p1-configuration, n = 6 and r = 1. Therefore

6 6!
No. of microstates = ( ) =
1 1! (6 − 1)!

6 6×5×4×3×2×1
( )=
1 1(5 × 4 × 3 × 2 × 1)

= 6 microstates

ii) For p2-configuration, n = 6 and r = 2. Therefore

6 6!
No. of microstates = ( ) =
2 2! (6 − 2)!

6 6×5×4×3×2×1
( )=
2 2 × 1(4 × 3 × 2 × 1)

= 15 microstates

iii) For d1-configuration, n = 10 and r = 1. Therefore

10 10!
No. of microstates = ( ) =
1 1! (10 − 1)!

10 10 × 9 × 8 × 7 × 6 × 5 × 4 × 3 × 2 × 1
( )=
1 1(9 × 8 × 7 × 6 × 5 × 4 × 3 × 2 × 1)

= 10 microstates

iv) For d2-configuration, n = 10 and r = 2. Therefore

10 10!
No. of microstates = ( ) =
2 2! (10 − 2)!

10 10 × 9 × 8 × 7 × 6 × 5 × 4 × 3 × 2 × 1
( )=
2 2 × 1(8 × 7 × 6 × 5 × 4 × 3 × 2 × 1)

= 45 microstates

The general form of atomic term symbols considers spin-spin (S-S coupling), orbital-orbital (L-L
coupling) and spin-orbital (L-S or Russell-Saunders coupling) interactions; therefore, before categorizing all
the microstates in these term symbols, it is extremely important to find out all possible microstates for different
electronic configurations. The total number of microstates for other different electronic configurations can be
calculated using the same method and are listed below.

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 CHAPTER 8 Electronic Spectra of Transition Metal Complexes: 217

Table 1. The calculated microstates for different electronic configurations.

Electronic configuration No. of microstates Electronic configuration No. of microstates

p1 6 d3 120

p2 15 d4 210

p3 20 d5 252

p4 15 d6 210

p5 6 d7 120

p6 1 d8 45

d1 10 d9 10

d2 45 d10 1

It can be seen that the number of microstates for the same number of unpaired electrons is equal. For example,
there are six microstates for p1 as well as p5 and forty-five microstates for both d2 as well as d8. It can be
explained in terms of electron-hole formalism which will be discussed later in this chapter.
2. When unpaired electrons are present in different subshell:
The same approach can also be applied to calculate the microstates in the case when the electrons are
present in two different subshells. Therefore, permutation and combination can be used to find out all these
numbers as follows:

𝑛 𝑚 𝑛! 𝑚!
No. of microstates = ( ) × ( ) = ×
𝑟 𝑠 (𝑛
𝑟! − 𝑟)! 𝑠! (𝑚 − 𝑠)!

Where, n is twice the number of orbitals and r is the number of unpaired electrons in one subshell while m is
twice the number of orbitals and s is the number of unpaired electrons in the other subshell. Now, the number
of microstates for different electronic configurations can be calculated easily.
i) p1p1-configuration, n = 6, r = 1, m = 6 and s = 1.

6 6 6! 6!
No. of microstates = ( ) × ( ) = ×
1 1 1! (6 − 1)! 1! (6 − 1)!

6 6 6×5×4×3×2×1 6×5×4×3×2×1
( )×( )= ×
1 1 1(5 × 4 × 3 × 2 × 1) 1(5 × 4 × 3 × 2 × 1)

= 36 microstates

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 218 A Textbook of Inorganic Chemistry – Volume I

ii) d1d1-configuration, n = 10, r = 1, m = 10 and s = 1.

10 10 10! 10!
No. of microstates = ( )×( )= ×
1 1 1! (10 − 1)! 1! (10 − 1)!

10 10 10 × 9 × 8 × 7 × 6 × 5 × 4 × 3 × 2 × 1 10 × 9 × 8 × 7 × 6 × 5 × 4 × 3 × 2 × 1
( )×( )= ×
1 1 1(9 × 8 × 7 × 6 × 5 × 4 × 3 × 2 × 1) 1(9 × 8 × 7 × 6 × 5 × 4 × 3 × 2 × 1)

= 100 microstates

iii) p1d1-configuration, n = 6, r = 1, m = 10 and s = 1.

6 10 6! 10!
No. of microstates = ( ) × ( ) = ×
1 1 1! (6 − 1)! 1! (10 − 1)!

6 10 6 × 5 × 4 × 3 × 2 × 1 10 × 9 × 8 × 7 × 6 × 5 × 4 × 3 × 2 × 1
( )×( )= ×
1 1 1(5 × 4 × 3 × 2 × 1) 1(9 × 8 × 7 × 6 × 5 × 4 × 3 × 2 × 1)

= 60 microstates

The total number of microstates for different electronic configurations can be calculated using the same method
and are listed below.

Table 2. The total number of microstates calculated for the different electronic configurations when
unpaired electrons are present in two different subshells.

Electronic configuration No. of microstates Electronic configuration No. of microstates

p1p1 36 d2d2 2025

p1p2 90 d2d3 5400

p2p2 225 p1d1 60

p2p3 300 p1d2 270

d1d1 100 p2d2 675

d1d2 450 p2d3 1800

This table can further be extended for the remaining combination of p-p, d-d, p-d or their
combinations with f-subshell. The number of microstates in particular configuration can be distributed to
various electronic states, represented by atomic term symbols. The distribution of these microstates in different
term symbols will be discussed later in this section.

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 CHAPTER 8 Electronic Spectra of Transition Metal Complexes: 219

 Atomic Term Symbols

Atomic term symbols may be defined as the symbolic representations of various electronic states
having different resultant angular momentums resulting from spin-spin, orbital-orbital or spin-orbital
interactions and the transitions between two different atomic states may also be represented using their term
symbols, to which certain rules apply.
The general form of any atomic term symbol that is used to represent any electronic state resulting
from inter-electronic repulsion is:

Where,
2S+1 = spin multiplicity
S = resultant spin angular momentum quantum number
L = resultant orbital angular momentum quantum number
J = resultant total angular momentum quantum number
Just like in the case of atomic orbitals, where l represents the individual orbital angular momentums; L
represents the resultants orbital angular momentum of an electronic state and gives the base designation of any
atomic term symbol.

L = 0 1 2 3 4 5 6 7

State = S P D F G H I K

The calculation of resultant spin and orbital angular momentum involves the concepts of space quantization
and vector interactions. A somewhat simplified approach for the calculation of resultant orbital angular
momentum quantum number (L), resultant spin angular momentum quantum number S and resultant total
angular momentum quantum number (J) can be given by understanding the spin-spin, orbital-orbital and spin-
orbital couplings schemes.
1. Orbital-orbital coupling (l-l interaction): Consider a multielectron system, then the resultant orbital
angular momentum quantum number can be deduced as:

L = (l1 + l2), (l1 + l2 −1) …….. ǀ l1 − l2 ǀ

Where l1 and l2 are the individual orbital angular momentum quantum numbers for electrons and modulus sign
shows that the value of resultant orbital angular momentum quantum number is always positive. Given the
eigenstates of l1 and l2, the construction of eigenstates of L (which still is conserved) is the coupling of the
angular momenta of electrons 1 and 2.

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 220 A Textbook of Inorganic Chemistry – Volume I

i) For p1p1-configuration, l1 = 1 and l2 = 1, therefore

L = (1 + 1), (1 + 1 −1), (1 −1)

L = 2, 1, 0

States = D, P, S

Similarly,
ii) For d1d1-configuration, l1 = 2 and l2 = 2, therefore

L = (2 + 2), (2 + 2 −1) ……. (2 −2)

L = 4, 3, 2, 1, 0

States = G, F, D, P, S

Although the above-mentioned procedure provides the resultant orbital angular momentum quantum
number (L) quite easily, the exact concept of orbital-orbital coupling can be understood only after knowing
the concepts of space quantization. One thing that is totally clear is that these symbols are nothing but the
mathematical shorthand of the electronic arrangements around the nucleus. The quantization of individual
orbital angular momentums can be used to calculate the resultant value as follows:
i) For p1p1-configuration, l1 = 1 and l2 = 1, therefore orbital angular momentum for each of the electron is √2
and it is a well-known fact from the quantum mechanics that √2 angular momentum can be oriented in space
with three different ways (+1, 0 and −1). The different combinations of orbital angular momentum can be
calculated as

l1(z) = +1 +1 +1 0 0 0 −1 −1 −1

l2(z) = +1 0 −1 +1 0 −1 +1 0 −1

Lz = +2 +1 0 +1 0 −1 0 −1 −2

Hence, the orbital angular momentums of two p-electrons can interact in nine ways, creating nine
combinations; out of which, three quantum-mechanically allowed series can be fashioned.

Lz = (+2, +1, 0, −1, −2), (+1, 0, −1), (0)

or

L = 2, 1, 0

Hence

States = D, P, S

Therefore, we can say that there are nine ways in which the orbital motion can interact.

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 CHAPTER 8 Electronic Spectra of Transition Metal Complexes: 221

Similarly,
ii) For d1d1-configuration, l1 = 2 and l2 = 2, therefore orbital angular momentum for each of the electron is √6
and it is a well-known fact from the quantum mechanics that √6 angular momentum can be oriented in space
with five different ways (+2, +1, 0, −1 and −2). The different combinations of orbital angular momentum can
be calculated as:

l1(z) = +2 +2 +2 +2 +2 +1 +1 +1 +1 +1

l2(z) = +2 +1 0 −1 −2 +2 +1 0 −1 −2

Lz = +4 +3 +2 +1 0 +3 +2 +1 0 −1

and

l1(z) = 0 0 0 0 0 −1 −1 −1 −1 −1

l2(z) = +2 +1 0 −1 −2 +2 +1 0 −1 −2

Lz = +2 +1 0 −1 −2 +1 0 −1 −2 −3

and

l1(z) = −2 −2 −2 −2 −2

l2(z) = +2 +1 0 −1 −2

Lz = 0 −1 −2 −3 −4

Hence, the orbital angular momentums of two d-electrons can interact in twenty-five ways, creating twenty-
five combinations; out of which, five quantum-mechanically allowed series can be fashioned.

Lz = (+4, +3, +2, +1, 0, −1, −2, −3, −4), (+3, +2, +1, 0, −1, −2, −3), (+2, +1, 0, −1, −2), (+1, 0, −1), (0)

or

L = 4, 3, 2, 1, 0

Which means

States = G, F, D, P, S

2. Spin-spin coupling (s-s interaction): Consider a multielectron system, then the resultant spin angular
momentum quantum number can be deduced as:

S = (s1 + s2), (s1 + s2 −1) …….. ǀ s1 − s2 ǀ

Where s1 and s2 are the individual spin angular momentum quantum numbers for electrons and modulus sign
shows that the value of resultant spin angular momentum quantum number is always positive.

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 222 A Textbook of Inorganic Chemistry – Volume I

i) For p1p1 or d1d1-configuration, s1 = 1/2 and s2 = 1/2, therefore

S = (1/2 + 1/2), (1/2 − 1/2)

or

S = 1, 0

Which means

Multiplicity = (2S + 1) = 3 and 1

The aforementioned procedure offers the resultant spin angular momentum quantum number (S)
quite easily but the exact concept of spin-spin interaction can be understood only after knowing the concepts
of space quantization. The quantization of individual spin angular momentums can be used to calculate the
resultant value as follows:
i) For p1p1 or d1d1-configuration, s1 = 1/2 and s2 = 1/2, therefore spin angular momentum for each of the
electrons is √0.75 and it is a well-known fact from the quantum mechanics that √0.75 angular momentum can
be oriented in space with two different ways (+1/2 and −1/2). The different combinations of spin angular
momentum can be calculated as:

s1(z) = +1/2 +1/2 −1/2 −1/2

s2(z) = +1/2 −1/2 +1/2 −1/2

Sz = +1 0 0 −1

Hence, the spin angular momentums of two p or d-electrons can interact in four ways, creating four
combinations; out of which, two quantum-mechanically allowed series can be fashioned.

Sz = (+1, 0, −1), (0)

or

S = 1, 0

Multiplicity = (2S + 1) = 3 and 1

The multiplicity actually represents the number of orientations possible for the total spin relative to the total
orbital angular momentum L, and thus to the number of near-degenerate levels that differ only in their spin-
orbit coupling energy. For example, the ground state of the carbon atom is a 3P state. The superscript of three
specifies that the multiplicity 2S+1 = 3 i.e. triplet, so that the total spin S = 1. This spin is due to two unpaired
electrons, as a result of Hund's rule which favors the single filling of degenerate orbitals. The spin multiplicity
is a primary factor in governing the overall energy of an electronic state and maybe summarised for different
electron combination.

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Table 3. Spin multiplicities for the different number of unpaired electron in an electronic configuration.

Unpaired Electrons S 2S+1 State

0 0 1 Singlet

1 1/2 2 Doublet

2 1 3 Triplet

3 3/2 4 Quartet

4 2 5 Quintet

3. Spin-orbital coupling (L-S interaction): In a multi-electron system, the resultant orbital angular
momentum (L) and resultant spin angular momentum (S) interact with each other to give total angular
momentum which is defined by the quantum number J.

J = (L + S), (L + S −1) …….. ǀ L − S ǀ

Where L and S are the quantum numbers for resultant orbital angular momentum and resultant spin angular
momentum, respectively. The modulus sign shows that the value of the resultant total angular momentum
quantum number is always positive. The value of J is assigned as the subscripts of the overall term symbol.
i) For p1p1-configuration, 9 combinations given by orbital-orbital coupling (L = 2, 1, 0) and 4 combinations
given by spin-spin coupling (S = 1, 0) combine to create a total of 36 microstates. therefore

L = 0, 1, 2 and S = 1, 0

States = 3S, 3P, 3D, 1S, 1P, 1D

The summarization of spin-orbital coupling for p1p1-configurations is given below.

Table 4. Splitting of the term symbols for p1p1-configuration due to L-S coupling.

State Value L and S Value of J States after L-S coupling

3
S L = 0 and S =1 J = (0 + 1) = 1 3
S1
3
P L = 1 and S = 1 J = (1 + 1) ….(1 – 1) = 3
P2, 3P1, 3P0
2, 1, 0

D
3
L = 2 and S = 1 J = (2 + 1) ….(2 – 1) = 3
D3, 3D2, 3D1
3, 2, 1

Table 4. Continued on the next page…

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 224 A Textbook of Inorganic Chemistry – Volume I

1
S L = 0 and S = 0 J = (0 + 0) = 0 1
S0
1
P state: L = 1 and S = 0 J = (1 + 0) = 1 1
P1
1
D state: L = 2 and S = 0 J = (2 + 0) = 2 1
D2

ii) For d1d1-configuration, 25 combinations given by orbital-orbital coupling (L = 4, 3, 2, 1, 0) and 4

combinations given by spin-spin coupling (S = 1, 0) couple to create a total of 100 microstates. therefore

L = 4, 3, 2, 1, 0

S = 1, 0

States = 3S, 3P, 3D, 3F, 3G, 1S, 1P, 1D, 1F, 1G

The summarization of spin-orbital coupling for d1d1-configurations is given below.

Table 5. Splitting of the term symbols for d1d1-configuration due to L-S coupling.

State Value L and S Value of J States after L-S coupling

3
S L = 0 and S =1 J = (0 + 1) = 1 3
S1
3
P L = 1 and S = 1 J = (1 + 1) ….(1 – 1) = 3
P2, 3P1, 3P0
2, 1, 0
3
D L = 2 and S = 1 J = (2 + 1) ….(2 – 1) = 3
D3, 3D2, 3D1
3, 2, 1
3
F L = 3 and S = 1 J = (3 + 1) ….(3 – 1) = 3
F4, 3F3, 3F2
4, 3, 2
3
G L = 4 and S = 1 J = (4 + 1) ….(4 – 1) = 3
G5, 3G4, 3G3
5, 4, 3
1
S L = 0 and S = 0 J = (0 + 0) = 0 1
S0
1
P L = 1 and S = 0 J = (1 + 0) = 1 1
P1
1
D L = 2 and S = 0 J = (2 + 0) = 2 1
D2
1
F L = 3 and S = 0 J = (3 + 0) = 3 1
F3
1
G L = 4 and S = 0 J = (4 + 0) = 4 1
G4

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 CHAPTER 8 Electronic Spectra of Transition Metal Complexes: 225

The quantization of individual orbital angular momentums can be used to calculate the resultant value
as follows: For 3P state of p1p1-configuration, L = 1 and S = 1. Therefore, the different combinations of resultant
orbital angular momentum and resultant spin angular momentum can be calculated:

Lz = +1 +1 +1 0 0 0 −1 −1 −1

Sz = +1 0 −1 +1 0 −1 +1 0 −1

Jz = +2 +1 0 +1 0 −1 0 −1 −2

Hence, the resultant orbital angular momentums and resultant spin angular momentums of 3P can interact in
nine ways, creating nine microstates; out of which, three quantum-mechanically allowed series can be
fashioned.

Jz = (+2, +1, 0, −1, −2), (+1, 0, −1), (0)

or

J = 2, 1, 0

Which means

States = 3P2, 3P1 and 3P0

 Derivation of the Term Symbols for Unpaired Electrons in the Same Subshell
In the previous section, we have distributed all the 36 microstates for p1p1-configuration in six
electronic states labeled by 3S, 3P, 3D, 1S, 1P and 1D term symbols. However, for p2-configuration (both of the
unpaired electrons in same subshell), many microstates that were possible in p1p1-configuration cannot exist if
they violate the Pauli exclusion principle. Therefore, there are only 15 microstates (complying with Pauli
principle) for p2-configuration which can be distributed in three electronic states labeled by 1S, 3P and 1D term
symbols.
Similarly, all the 100 microstates for d1d1-configuration (3S, 3P, 3D, 3F, 3G, 1S, 1P, 1D, 1F and 1G)
cannot exist if they both the electrons are present in the same d-subshell. Therefore, there are only 45
microstates (complying with Pauli principle) for d2-configuration which can be distributed in five electronic
states labeled by 1S, 3P, 1D, 3F and 1G term symbols.
Term symbols for electronic configurations with unpaired electrons in the same subshell can be
derived using “pigeon hole” diagrams. The principal steps for such operations are:
1. Create vertical columns for all allowed orientation or effect of individual orbital angular momentum in the
reference direction. For example, +1, 0 and −1 are the allowed orientations of the orbital angular momentum
corresponding to l = 1 value.
2. Fill up the electrons in these columns by exhausting all the possibilities of parallel, paired and opposite
orientations.

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3. Sum-up all the lz values of every column to find out the resultant Lz values.
4. Quantum mechanically allowed series set-up should be carried out for different parallel, paired and opposite
orientation, which in turn can be used to provide the resultant orbital angular momentum quantum number L
for particular resultant spin quantum number S.
5. Combine the values of L and S to find out the term symbols for allowed electronic states.
1. s1-configuration:

lz

0 ↑

Lz 0

As Lz = 0, the value of resultant orbital angular momentum quantum number L = 0. There is only one unpaired
electron, therefore S = 1/2.
From L = 0, the state is S; and from S = 1/2, the multiplicity is 2. Thus, the overall term symbol is 2S.
2. s2-configuration:

lz

0 ↑↓

Lz 0

As Lz = 0, the value of resultant orbital angular momentum quantum number L = 0. There are no unpaired
electrons, therefore S = 0.
From L = 0, the state is S; and from S = 0, the multiplicity is 1. Thus, the overall term symbol is 1S.
3. p1 and p5-configuration:

lz

−1 ↑

0 ↑

+1 ↑

Lz +1 0 −1

As Lz = +1, 0, −1; the value of resultant orbital angular momentum quantum number L = 1. There is one
unpaired electron, therefore S = 1/2.
From L = 1, the state is P; and from S = 1/2, the multiplicity is 2. Thus, the overall term symbol is 2P. Hence,
all the 6 microstates for p1 and p5-configurations are distributed in 2P term symbol.

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4. p2 and p4-configuration:
For parallel arrangements,

lz

−1 ↑ ↑

0 ↑ ↑

+1 ↑ ↑

Lz +1 0 −1

As Lz = +1, 0, −1; the value of resultant orbital angular momentum quantum number L = 1.
There are two unpaired electrons, therefore S = 1.
From L = 1, the state is P.
From S = 1, the multiplicity is 3.
Thus, the overall term symbol is 3P.
Similarly,
For paired and opposite arrangements,

lz

−1 ↑↓ ↓ ↓

0 ↑↓ ↓ ↑

+1 ↑↓ ↑ ↑

Lz +2 0 −2 +1 0 −1

Out of six values of Lz (resultant orbital angular momentum in reference direction), two quantum-mechanically
allowed series can be setup. One with Lz = +2, +1, 0, −1, −2; giving resultant orbital angular momentum
quantum number L = 2. The second series with Lz = 0; giving resultant orbital angular momentum quantum
number L = 0.
There are zero unpaired electrons, therefore S = 0.
From L = 2 and 0; the states are D and S, respectively.
From S = 0, the multiplicity is 1.
Thus, the overall term symbols are 1D and 1S.
Hence, all the 15 microstates for p2 and p4 electronic configurations which can be distributed in 1S, 3P and 1D
term symbols.

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5. p3-configuration:

lz

−1 ↑ ↑ ↑ ↑↓ ↑↓ ↓ ↓

0 ↑ ↑ ↑↓ ↑↓ ↑ ↑ ↓

+1 ↑ ↑↓ ↑↓ ↑ ↑ ↑ ↑

Lz 0 +2 +1 −1 +1 −1 −2 0 0

Parallel Paired and opposite

For parallel arrangements,

As Lz = 0; the value of resultant orbital angular momentum quantum number L = 0. There are three unpaired
electrons, therefore S = 3/2.
From L = 0, the state is S; and from S = 3/2, the multiplicity is 4. Thus, the overall term symbol is 4S.
For paired and opposite arrangements,
Out of eight values of Lz, two quantum-mechanically allowed series can be setup. One with Lz = +2, +1, 0, −1,
−2; giving resultant orbital angular momentum quantum number L = 2. The second series with Lz = +1, 0, −1;
giving resultant orbital angular momentum quantum number L = 1. There is one unpaired electron, therefore
S = 1/2.
From L = 2 and 1 the states are D and P, respectively.
From S = 1/2, the multiplicity is 2.
Thus, the overall term symbols are 2D and 2P.
Hence, all the 20 microstates for p3-configurations are distributed in 4S, 2P and 2D term symbols.
6. p6-configuration:

lz

−1 ↑↓

0 ↑↓

+1 ↑↓

Lz 0

As Lz = 0, the value of resultant orbital angular momentum quantum number L = 0; and zero unpaired electrons,
therefore S = 0. Thus, the overall term symbol is 1S which contains the one and only microstate of p6-electronic
configuration.

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7. d1 and d9-configuration:

lz

−2 ↑

−1 ↑

0 ↑

+1 ↑

+2 ↑

Lz +2 +1 0 −1 −2

As Lz = +2, +1, 0, −1, −2; the value of resultant orbital angular momentum quantum number L = 2.
There is only one unpaired electron, therefore S = 1/2.
From L = 2, the state is D; and from S = 1/2, the multiplicity is also 2.
Thus, the overall term symbol is 2D.
Hence, all the 10 microstates for d1 and d9-configurations are distributed in 2D term symbols.
8. d2 and d8-configuration:
For parallel arrangements,

lz

−2 ↑ ↑ ↑ ↑

−1 ↑ ↑ ↑ ↑

0 ↑ ↑ ↑ ↑

+1 ↑ ↑ ↑ ↑

+2 ↑ ↑ ↑ ↑

Lz +3 +2 +1 0 +1 0 −1 −1 −2 −3

Out of ten values of Lz, two quantum-mechanically allowed series can be setup. One with Lz = +3, +2, +1, 0,
−1, −2, −3; giving resultant orbital angular momentum quantum number L = 3. The second series with L z =
+1, 0, −1; giving resultant orbital angular momentum quantum number L = 1. There are two unpaired electrons,
therefore S = 1.
From L = 3 and 1, the states are F and P, respectively. From S = 1, the multiplicity is 3. Thus, the overall term
symbols are 3F and 3P.

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For paired and opposite arrangements,

lz

−2 ↑↓ ↓ ↓ ↓ ↓

−1 ↑↓ ↓ ↓ ↓ ↑

0 ↑↓ ↓ ↓ ↑ ↑

+1 ↑↓ ↓ ↑ ↑ ↑

+2 ↑↓ ↑ ↑ ↑ ↑

Lz +4 +2 0 −2 −4 +3 +2 +1 0 +1 0 −1 −1 −2 −3

Out of fifteen values of Lz, three quantum-mechanically allowed series can be setup. First with Lz = +4, +3,
+2, +1, 0, −1, −2, −3, −4; giving resultant orbital angular momentum quantum number L = 4. Second series
with Lz = +2, +1, 0, −1, −2; giving resultant orbital angular momentum quantum number L = 2. The third series
with Lz = 0; giving resultant orbital angular momentum quantum number L = 0. There are zero unpaired
electrons, therefore S = 0.
From L = 4, 2 and 0 the states are G, D and S, respectively. From S = 0, the multiplicity is 1. Thus, the overall
term symbols are 1G, 1D and 1S.
Hence, all the 45 microstates for d2 and d8-configurations are distributed in 1S, 3P, 1D, 3F and 1G term symbols.
9. d3 and d7-configuration:
For parallel arrangements,

lz

−2 ↑ ↑ ↑ ↑ ↑ ↑

−1 ↑ ↑ ↑ ↑ ↑ ↑

0 ↑ ↑ ↑ ↑ ↑ ↑

+1 ↑ ↑ ↑ ↑ ↑ ↑

+2 ↑ ↑ ↑ ↑ ↑ ↑

Lz +3 +2 +1 0 −1 −3 +1 −1 −2 0

Out of ten values of Lz, two quantum-mechanically allowed series can be setup.
One with Lz = +3, +2, +1, 0, −1, −2, −3; giving resultant orbital angular momentum quantum number L = 3.
The second series with Lz = +1, 0, −1; giving resultant orbital angular momentum quantum number L = 1.
There are three unpaired electrons, therefore S = 3/2.
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 CHAPTER 8 Electronic Spectra of Transition Metal Complexes: 231

From L = 3 and 1; the states are F and P, respectively. From S = 3/2, the multiplicity is 4. Thus, the overall
term symbols are 4F and 4P.
For paired and opposite arrangements,

lz

−2 ↑ ↑ ↑ ↑

−1 ↑ ↑ ↑ ↑↓ ↑↓ ↑↓

0 ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑

+1 ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑

+2 ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑

Lz +5 +4 +3 +2 +2 +1 0 +4 −1 −2 +1 +2 −4 −2 −1

and

lz

−2 ↑↓ ↑↓ ↑↓ ↑↓ ↓ ↓ ↓ ↓ ↓ ↓

−1 ↑↓ ↑ ↓ ↓ ↑ ↓ ↑ ↑

0 ↑ ↓ ↑ ↑ ↑ ↑ ↑

+1 ↑ ↑ ↑ ↑ ↑ ↑ ↑

+2 ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑

Lz 0 −5 −4 −3 −2 +3 +2 +1 0 −1 −3 +1 −1 −2 0

Out of thirty values of Lz, six quantum-mechanically allowed series can be setup. First with Lz = +5, +4, +3,
+2, +1, 0, −1, −2, −3, −4, −5; giving resultant orbital angular momentum quantum number L = 5. Second series
with Lz = +4, +3, +2, +1, 0, −1, −2, −3, −4; giving resultant orbital angular momentum quantum number L =
4. The third series with Lz = +3, +2, +1, 0, −1, −2, −3; giving resultant orbital angular momentum quantum
number L = 3. Fourth and fifth series with Lz = +2, +1, 0, −1, −2; giving resultant orbital angular momentum
quantum number L = 2 and 2, respectively. The sixth series is consisted of L z = +1, 0, −1; giving resultant
orbital angular momentum quantum number L = 1.
There is one unpaired electron, therefore S = 1/2.
From L = 5, 4, 3, 2, 2 and 1; the states are H, G, F, D, D and P, respectively.
From S = 1/2, the multiplicity is 2.

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 232 A Textbook of Inorganic Chemistry – Volume I

Thus, the overall term symbols are 2H, 2G, 2F, 2D, 2D and 2P.
Hence, all the 120 microstates for d3 and d7-configurations are distributed in 4F, 4P, 2H, 2G, 2F, 2D, 2D and 2P
term symbols.
10. d4 and d6-configuration:
For parallel arrangements,

lz

−2 ↑ ↑ ↑ ↑

−1 ↑ ↑ ↑ ↑

0 ↑ ↑ ↑ ↑

+1 ↑ ↑ ↑ ↑

+2 ↑ ↑ ↑ ↑

Lz +2 +1 0 −1 −2

Out of five values of Lz, only one quantum-mechanically allowed series can be set up with Lz = +2, +1, 0, −1,
−2; giving resultant orbital angular momentum quantum number L = 2.
There are four unpaired electrons, therefore S = 2.
From L = 2, the state is D.
From S = 2, the multiplicity is 5.
Thus, the overall term symbol is 5D.
For two electrons paired or opposite arrangement,

lz

−2 ↑ ↑ ↑ ↑ ↑ ↑ ↑

−1 ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑

0 ↑ ↑ ↑ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓

+1 ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑

+2 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑ ↑ ↑

Lz +5 +4 +2 +3 +2 +1 +1 0 −1 +4 +3 +2 −3 +3 +1

and

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 CHAPTER 8 Electronic Spectra of Transition Metal Complexes: 233

lz

−2 ↑ ↑ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

−1 ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑

0 ↑↓ ↑↓ ↑↓ ↑ ↑ ↑ ↑ ↑ ↑

+1 ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑

+2 ↑ ↑ ↑ ↑ ↑ ↑ ↑

Lz 0 0 −1 +1 0 −2 −1 −3 −4 −1 −2 −3 −3 −4 −5

and

lz

−2 ↓ ↓ ↓ ↓ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑

−1 ↓ ↑ ↑ ↑ ↑ ↑ ↓ ↓ ↑ ↑ ↑ ↑

0 ↑ ↑ ↑ ↑ ↓ ↓ ↑ ↑ ↑ ↑ ↓ ↓

+1 ↑ ↑ ↑ ↑ ↑ ↑ ↓ ↑ ↓ ↓ ↓ ↑

+2 ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑

Lz +2 +1 0 −1 −2 +2 +1 0 −1 −2 +2 +1 0 −1 −2

Out of forty-five values of Lz, seven quantum-mechanically allowed series can be setup as. First with Lz = +5,
+4, +3, +2, +1, 0, −1, −2, −3, −4, −5; giving resultant orbital angular momentum quantum number L = 5.
Second series with Lz = +4, +3, +2, +1, 0, −1, −2, −3, −4; giving resultant orbital angular momentum quantum
number L = 4. The third and fourth series with Lz = +3, +2, +1, 0, −1, −2, −3; giving resultant orbital angular
momentum quantum number L = 3 and 3. fifth series with Lz = +2, +1, 0, −1, −2; giving resultant orbital
angular momentum quantum number L = 2. The sixth and seventh series is consisted of Lz = +1, 0, −1; giving
resultant orbital angular momentum quantum number L = 1 and 1, respectively.
There are two unpaired electrons, therefore S = 1.
From L = 5, 4, 3, 3, 2, 1 and 1; the states are H, G, F, F, D, P and P, respectively.
From S = 1, the multiplicity is 3.
Thus, the overall term symbols are 3H, 3G, 3F, 3F, 3D, 3P and 3P.
Similarly,
For all electrons paired or opposite arrangement,

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 234 A Textbook of Inorganic Chemistry – Volume I

lz

−2 ↑↓ ↑↓ ↑↓ ↑↓ ↓ ↓

−1 ↑↓ ↑↓ ↑↓ ↑↓ ↓ ↓

0 ↑↓ ↑↓ ↑↓ ↑↓ ↓ ↑ ↑

+1 ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑

+2 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

Lz +6 +4 +2 0 +1 0 −2 −2 −4 −6 +5 +4 +2 +3 +2

and

lz

−2 ↓ ↓ ↓ ↓ ↓ ↓ ↓

−1 ↑ ↓ ↑ ↓ ↑ ↓ ↓ ↑↓ ↑↓

0 ↑ ↑ ↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↓

+1 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↓ ↑ ↑ ↓

+2 ↑↓ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑

Lz +1 +1 0 −1 +4 +3 +2 −3 +3 +1 0 0 −1 +1 0

and

lz

−2 ↓ ↓ ↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↓ ↓ ↓ ↓

−1 ↑↓ ↑↓ ↑↓ ↑↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓

0 ↓ ↑ ↓ ↓ ↑ ↓ ↓ ↑ ↑

+1 ↑ ↑ ↓ ↑ ↑ ↑ ↑ ↑ ↑

+2 ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑

Lz −2 −1 −3 −4 −1 −2 −3 −3 −4 −5 +2 +1 0 −1 −2

and

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 CHAPTER 8 Electronic Spectra of Transition Metal Complexes: 235

lz

−2 ↓ ↓ ↓ ↓

−1 ↓ ↑ ↑ ↑

0 ↑ ↑ ↓ ↓

+1 ↓ ↓ ↓ ↑

+2 ↑ ↑ ↑ ↑

Lz +2 +1 0 −1 −2

Out of fifty values of Lz, eight quantum-mechanically allowed series can be setup as. First with Lz = +6, +5,
+4, +3, +2, +1, 0, −1, −2, −3, −4, −5, −6; giving resultant orbital angular momentum quantum number L = 6.
Second and third series with Lz = +4, +3, +2, +1, 0, −1, −2, −3, −4; giving resultant orbital angular momentum
quantum number L = 4 and 4, respectively. The fourth series with Lz = +3, +2, +1, 0, −1, −2, −3; giving
resultant orbital angular momentum quantum number L = 3. Fifth and sixth series with Lz = +2, +1, 0, −1, −2;
giving resultant orbital angular momentum quantum number L = 2 and 2, respectively. The seventh and eighth
series is consisted of Lz = 0; giving resultant orbital angular momentum quantum number L = 0 and 0,
respectively. There are zero unpaired electrons, therefore S = 0.
From L = 6, 4, 4, 3, 2, 2, 0 and 0; the states are I, G, G, F, D, D, S and S, respectively. From S = 0, the
multiplicity is 1. Thus, the overall term symbols are 1I, 1G, 1G, 1F, 1D, 1D, 1S and 1S.
Hence, all the 210 microstates for d4 and d6-configurations are distributed in 5D, 3H, 3G, 3F, 3F, 3D, 3P, 3P, 1I,
1
G, 1G, 1F, 1D, 1D, 1S and 1S term symbols.
11. d5-configuration:
For parallel arrangements,

lz

−2 ↑

−1 ↑

0 ↑

+1 ↑

+2 ↑

Lz 0

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 236 A Textbook of Inorganic Chemistry – Volume I

As Lz = 0; the value of resultant orbital angular momentum quantum number L = 0. There are five unpaired
electrons, therefore S = 5/2.
From L = 0, the state is S. From S = 5/2, the multiplicity is 6. Thus, the overall term symbol is 6S.
For two electrons paired or opposite arrangement,

lz

−2 ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑

−1 ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓

0 ↑ ↑ ↑ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑

+1 ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑ ↑ ↑

+2 ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑

Lz +4 +3 +2 +1 +3 +2 +1 −1 +2 +1 −1 −2 +1 −1 −2

and

lz

−2 ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↓ ↑ ↑ ↑

−1 ↑↓ ↑ ↑ ↑ ↑ ↓ ↑ ↑

0 ↑ ↑ ↑ ↑ ↑ ↑ ↓ ↑

+1 ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↓

+2 ↑ ↑ ↑ ↑ ↑ ↑ ↑

Lz −3 −1 −2 −3 −4 0 0 0 0

Out of twenty-four values of Lz, four quantum-mechanically allowed series can be setup as. First with Lz = +4,
+3, +2, +1, 0, −1, −2, −3, −4; giving resultant orbital angular momentum quantum number L = 4. Second series
with Lz = +3, +2, +1, 0, −1, −2, −3; giving resultant orbital angular momentum quantum number L = 3. The
third series with Lz = +2, +1, 0, −1, −2; giving resultant orbital angular momentum quantum number L = 3.
The fourth series is consisted of Lz = +1, 0, −1; giving resultant orbital angular momentum quantum number
L = 1.
There are three unpaired electrons, therefore S = 3/2.
From L = 4, 3, 2 and 1; the states are G, F, D and P, respectively.
From S = 3/2, the multiplicity is 4.
Thus, the overall term symbols are 4G, 4F, 4D and 4P.
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 CHAPTER 8 Electronic Spectra of Transition Metal Complexes: 237

For four electrons paired or opposite arrangement,

lz

−2 ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑

−1 ↑ ↑ ↑↓ ↑↓ ↑↓ ↑ ↑

0 ↑ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑↓ ↑↓ ↑↓

+1 ↑↓ ↑↓ ↑↓ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓

+2 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑

Lz +6 +5 +4 +5 +3 +2 +3 +2 0 +1 0 −1 +4 +1 0

and

lz

−2 ↑ ↑↓ ↑↓ ↑↓ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

−1 ↑↓ ↑↓ ↑↓ ↑ ↑↓ ↑↓ ↑↓ ↑ ↑↓ ↑↓ ↑↓

0 ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑

+1 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑

+2 ↑ ↑ ↑ ↑ ↑

Lz +2 0 −2 0 −2 −3 0 −1 −4 −2 −3 −5 −4 −5 −6

and

lz

−2 ↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓

−1 ↓ ↑ ↑ ↓ ↑ ↑ ↓ ↑ ↑ ↑↓ ↑↓ ↑↓

0 ↑ ↑ ↑ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↓ ↑

+1 ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑ ↑ ↑

+2 ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑

Lz +4 +3 +2 +1 +3 +2 +1 −1 +2 +1 −1 −2 +1 −1 −2

and

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 238 A Textbook of Inorganic Chemistry – Volume I

lz

−2 ↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑ ↑ ↑ ↑ ↑

−1 ↑↓ ↓ ↓ ↓ ↑ ↓ ↓ ↑ ↓ ↓ ↑

0 ↑ ↓ ↑ ↑ ↓ ↓ ↑ ↓ ↓ ↑ ↑↓ ↑↓

+1 ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↓ ↓

+2 ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑ ↑ ↑

Lz −3 −1 −2 −3 −4 +4 +3 +2 +1 +3 +2 +1 −1 +2 +1

and

lz

−2 ↑ ↑ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↓ ↑ ↑ ↑ ↑

−1 ↓ ↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑ ↓ ↓ ↑ ↑ ↓

0 ↑↓ ↑↓ ↑ ↓ ↓ ↑ ↓ ↓ ↑ ↓ ↓ ↑ ↑

+1 ↑ ↓ ↓ ↑ ↓ ↓ ↑ ↑ ↑ ↓ ↓ ↓

+2 ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↓ ↑

Lz −1 −2 +1 −1 −2 −3 −1 −2 −3 −4 0 0 0 0 0

Out of seventy-five values of Lz, eleven quantum-mechanically allowed series can be setup. First with Lz = +6,
+5, +4, +3, +2, +1, 0, −1, −2, −3, −4, −5, −6; giving resultant orbital angular momentum quantum number L
= 6. Second series with Lz = +5, +4, +3, +2, +1, 0, −1, −2, −3, −4 −5; giving resultant orbital angular momentum
quantum number L = 5. The third and fourth series with Lz = +4, +3, +2, +1, 0, −1, −2, −3, −4; giving resultant
orbital angular momentum quantum number L = 4. Fifth and sixth series with Lz = +3, +2, +1, 0, −1, −2, −3;
giving resultant orbital angular momentum quantum number L = 3 and 3, respectively. The seventh, eighth
and ninth series are consisted of Lz = +2, +1, 0, −1, −2; giving resultant orbital angular momentum quantum
number L = 2, 2 and 2, respectively. The tenth and eleventh series are consisted of Lz = +1, 0, −1 and Lz = 0;
giving resultant orbital angular momentum quantum number L = 1 and 0, respectively.
There is one unpaired electron which S = 1/2.
From L = 6, 5, 4, 4, 3, 3, 2, 2, 2, 1 and 0; the states are I, H, G, G, F, F, D, D, D, P and S, respectively. From
S = 1/2, the multiplicity is 2. Thus, the overall term symbols are 2I, 2H, 2G, 2G, 2F, 2F, 2D, 2D, 2D, 2P and 2S.
Hence, all the 252 microstates for d5-configurations are distributed in 2I, 2H, 2G, 2G, 2F, 2F, 2D, 2D, 2D, 2P, 2S,
4
G, 4F, 4D, 4P and 6S term symbols.

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 CHAPTER 8 Electronic Spectra of Transition Metal Complexes: 239

12. d10-configuration:

lz

−2 ↑↓

−1 ↑↓

0 ↑↓

+1 ↑↓

+2 ↑↓

Lz 0

As Lz = 0; the value of resultant orbital angular momentum quantum number L = 0. There are no unpaired
electrons, therefore S = 0.
From L = 0, the state is S. From S = 0, the multiplicity is 1. Thus, the overall term symbol is 1S which contains
the only microstate of d10-configuration.
It can clearly be seen that the number of microstates, as well as the term symbols for dn and d10−n
configurations, are the same. This is due to the fact that the number of unpaired electrons is the same for both
of the configurations. In other words, the possible arrangements for unpaired electrons in less than half-filled
or for holes in more than half-filled configurations are the same. The same analogy is true for s, p or f-subshell.
Moreover, the number of microstates distributed in any term symbol can be calculated using the
following relations:
1. Term symbols without J-value: (2L+1) × (2S+1)
2. Term symbols without J-value: (2J+1)
Let us tally the number of microstates for p2 electronic configuration with term symbols distribution.

(2L+1) × (2S+1) (2J+1)

Distribution 1
S = (2×0+1) × (2×0+1) = 1 1
S0 = 2×0 + 1 = 1
of 15
microstates → 3
P = (2×1+1) × (2×1+1) = 9 3
P2 = 2×2 + 1 = 5
of p2-
configuration
1
D = (2×2+1) × (2×0+1) = 5 3
P1 = 2×1 + 1 = 3
in 1S, 3P, 1D
3
P0 = 2×0 + 1 = 1
term symbols
1
D2 = 2×2 + 1 = 5

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 240 A Textbook of Inorganic Chemistry – Volume I

 Determination of Spectroscopic Ground State Term

In a particular configuration, the classification of various microstates in different term symbols also
distinguishes them energetically. It can be explained in terms of the effect of spin-spin, orbital-orbital and spin-
orbital coupling. There are two different approaches, both are based upon some conclusive results from
quantum mechanics, to find out the term symbol for ground electronic state.
1. From correlation diagram: This approach is based on the correlation of all the free ion term of a particular
atom or ion and then the ground state term is calculated with the help of certain rules.
i) The energy of different terms (electronic states) depends primarily on the Hund’s rule, which states that the
most stable state should have the highest multiplicity. Hence, triplet states are more stable than the singlet one.
In other words, the higher the value of 2S+1, the greater will be the stability.
ii) If the value of spin multiplicities for two different states is the same, the value of resultant angular
momentum will the deciding factor in the determination of the lower energy term. A higher value of L gives
the lower energy state and the vice-versa is also true.
iii) The energy dependence of different terms upon total angular momentum is configuration-specific in nature.
The perturbed Hamiltonian of spin-orbital interaction can have both types of effect, stabilization or
destabilization, over the energy states and depends upon the magnitude of J-value. It has been proved that the
interaction of spin-orbital motion destabilizes the less than half filed configuration and stabilizes the more than
half-filled. Hence, a lower J-value for less than half-filled and a higher J-value of more than half will give the
lower energy.
Let us apply this procedure to find out the ground state term symbol for p2-configuration:

Figure 1. Splitting of free ion terms in the carbon atom.

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 CHAPTER 8 Electronic Spectra of Transition Metal Complexes: 241

The effect of spin-spin interaction makes the triplet (3P) state more stable in comparison to the singlet
1
D or 1S. Furthermore, the stabilization of 1D state after the consideration of orbital-orbital interaction can be
attributed to the higher value of orbital angular momentum. Finally, as the p2-configuration is less than half-
filled; the splitting of 3P state goes with 3P0 as the ground state term symbol.
2. Using L-S coupling scheme: This procedure is applicable only to find out the ground state term symbol.
We do not need to calculate all the microstates but only present in the ground electronic state. Various steps
involved in this procedure are:
1. The electron filling in the valence subshell should be carried out in such a way that a maximum spin
multiplicity (2S+1) is produced.
2. Maximize the value of resultant orbital angular momentum component by filing electrons first in the orbitals
with the positive component of individual orbital angular momentum.
3. Select maximum J-value for more than half-filled and minimum J-value for less than half-filled
configuration.
Let us determine the ground state term symbol for carbon atom. The electronic configuration for
carbon is 1s2, 2s2, 2p2.

lz +1 0 −1

2p ↑ ↑

From the total component of orbital and spin angular momentum, L = (+1) + (0) = 1 and S = 1/2 + 1/2 = 1.
From L-S coupling, ǀL+Sǀ ...… ǀL−Sǀ; (1+1) …. (1 −1) = 2, 1, 0.
Now, as the configuration is less than half-filled, the lower J-value is selected for lower energy. Thus, this
gives rise to a 3P0 state.
For nitrogen atom, the determination of the ground state term symbol can be calculated through the
same route. The electronic configuration for nitrogen is 1s2, 2s2, 2p3.

lz +1 0 −1

2p ↑ ↑ ↑

From the total component of orbital and spin angular momentum, L = (+1) + (0) + (−1) = 0 and S = 1/2 + 1/2
+ 1/2 = 3/2.
From L-S coupling, ǀL+Sǀ ...… ǀL−Sǀ; (0 + 3/2) = 3/2.
Now, as the configuration is half-filled, the only J-value is bound to be selected for lower energy. Thus, this
gives rise to a 4S3/2 state.
For trivalent vanadium ion (V3+), the electronic configuration can be given as is 1s2, 2s2, 2p6, 3s2, 3p6,
4s0, 3d2.

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 242 A Textbook of Inorganic Chemistry – Volume I

lz +2 +1 0 −1 −2

3d ↑ ↑

From the total component of orbital and spin angular momentum, L = (+2) + (+1) = 3 and S = 1/2 + 1/2 = 1.
From L-S coupling, ǀL+Sǀ ...… ǀL−Sǀ; (3 + 1) …. (3 − 1) = 4, 3, 2. Now, as the configuration is less than half-
filled, the lower J-value is selected for lower energy. Thus, this gives rise to a 3F2 state. However, the ground
state term symbol for d8-configuration will be 3F4.
All the free ions terms (including ground states) for different electronic configurations are
summarized in the following table. However, it must be kept in mind that the ground state term symbol after
L-S coupling will be different for more than half-filled and less than half-filled counterparts.

Table 6. The free ion terms and the corresponding ground electronic states for different types of electronic
configuration.

Electronic Free ion terms Ground State

configuration

s1 2
S 2
S

s2 1
S 1
S

p1, p5 2
P 2
P

p2, p4 1
S, 3P, 1D 3
P

p3 4
S, 2P, 2D 4
S

p6 1
S 1
S

d1, d9 2
D 2
D

d2, d8 1
S, 3P, 1D, 3F, 1G 3
F

d3, d7 4
F, 4P, 2H, 2G, 2F, 2D, 2D, 2P 4
F

d4, d6 5
D, 3H, 3G, 3F, 3F, 3D, 3P, 3P, 1I, 1G, 1G, 1F, 1D, 1D, 1S, 1S 5
D

d5 2
I, 2H, 2G, 2G, 2F, 2F, 2D, 2D, 2D, 2P, 2S, 4G, 4F, 4D, 4P, 6S 6
S

d10 1
S 1
S

It is also worthy to note that the ground state term symbol for all fully-filled subshells like s2, p6, or d10 is 1S
always which also includes the one and only microstate available.

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Table of Contents
CHAPTER 1 ..................................................................................................................................... 11
Stereochemistry and Bonding in Main Group Compounds: ........................................................ 11
 VSEPR Theory ................................................................................................................................ 11
 dπ–pπ Bonds .................................................................................................................................... 23
 Bent Rule and Energetic of Hybridization....................................................................................... 28
 Problems .......................................................................................................................................... 42
 Bibliography .................................................................................................................................... 43

CHAPTER 2 ..................................................................................................................................... 44
Metal-Ligand Equilibria in Solution:................................................................................................. 44
 Stepwise and Overall Formation Constants and Their Interactions ................................................ 44
 Trends in Stepwise Constants .......................................................................................................... 46

 Factors Affecting Stability of Metal Complexes with Reference to the Nature of Metal Ion and
Ligand .............................................................................................................................................. 49
 Chelate Effect and Its Thermodynamic Origin................................................................................ 56
 Determination of Binary Formation Constants by pH-metry and Spectrophotometry .................... 63
 Problems .......................................................................................................................................... 68
 Bibliography .................................................................................................................................... 69

CHAPTER 3 ..................................................................................................................................... 70
Reaction Mechanism of Transition Metal Complexes – I: ............................................................ 70
 Inert and Labile Complexes............................................................................................................. 70
 Mechanisms for Ligand Replacement Reactions ............................................................................ 77
 Formation of Complexes from Aquo Ions ....................................................................................... 82
 Ligand Displacement Reactions in Octahedral Complexes- Acid Hydrolysis, Base Hydrolysis .... 86
 Racemization of Tris Chelate Complexes ....................................................................................... 89
 Electrophilic Attack on Ligands ...................................................................................................... 92
 Problems .......................................................................................................................................... 94
 Bibliography .................................................................................................................................... 95
CHAPTER 4 ..................................................................................................................................... 96
Reaction Mechanism of Transition Metal Complexes – II:...................................................... 96
 Mechanism of Ligand Displacement Reactions in Square Planar Complexes ................................ 96
 The Trans Effect .............................................................................................................................. 98
 Theories of Trans Effect ................................................................................................................ 103

 Mechanism of Electron Transfer Reactions – Types; Outer Sphere Electron Transfer Mechanism and
Inner Sphere Electron Transfer Mechanism .................................................................................. 106
 Electron Exchange ......................................................................................................................... 117
 Problems ........................................................................................................................................ 121
 Bibliography .................................................................................................................................. 122

CHAPTER 5 ................................................................................................................................... 123

Isopoly and Heteropoly Acids and Salts: ........................................................................................ 123
 Isopoly and Heteropoly Acids and Salts of Mo and W: Structures of Isopoly and Heteropoly
Anions ............................................................................................................................................123
 Problems ........................................................................................................................................ 152
 Bibliography .................................................................................................................................. 153

CHAPTER 6 ................................................................................................................................... 154

Crystal Structures: ............................................................................................................................... 154
 Structures of Some Binary and Ternary Compounds Such as Fluorite, Antifluorite, Rutile, Antirutile,
Crystobalite, Layer Lattices - CdI2, BiI3; ReO3, Mn2O3, Corundum, Pervoskite, Ilmenite and
Calcite.............................................................................................................................................154

 Problems ........................................................................................................................................ 178

 Bibliography .................................................................................................................................. 179

CHAPTER 7 ................................................................................................................................... 180

Metal-Ligand Bonding: ....................................................................................................................... 180
 Limitation of Crystal Field Theory ................................................................................................ 180
 Molecular Orbital Theory – Octahedral, Tetrahedral or Square Planar Complexes...................... 184
 π-Bonding and Molecular Orbital Theory ..................................................................................... 198
 Problems ........................................................................................................................................ 212
 Bibliography .................................................................................................................................. 213
CHAPTER 8 ................................................................................................................................... 214
Electronic Spectra of Transition Metal Complexes: .................................................................... 214
 Spectroscopic Ground States ......................................................................................................... 214
 Correlation and Spin-Orbit Coupling in Free Ions for 1st Series of Transition Metals ................. 243
 Orgel and Tanabe-Sugano Diagrams for Transition Metal Complexes (d1 – d9 States) ................ 248
 Calculation of Dq, B and β Parameters ......................................................................................... 280
 Effect of Distortion on the d-Orbital Energy Levels ..................................................................... 300
 Structural Evidence from Electronic Spectrum ............................................................................. 307
 Jahn-Tellar Effect .......................................................................................................................... 312
 Spectrochemical and Nephelauxetic Series ................................................................................... 324
 Charge Transfer Spectra ................................................................................................................ 328
 Electronic Spectra of Molecular Addition Compounds................................................................. 336
 Problems ........................................................................................................................................ 340
 Bibliography .................................................................................................................................. 341

CHAPTER 9 ................................................................................................................................... 342

Magnetic Properties of Transition Metal Complexes: ................................................................. 342
 Elementary Theory of Magneto-Chemistry ................................................................................... 342
 Guoy’s Method for Determination of Magnetic Susceptibility ..................................................... 351
 Calculation of Magnetic Moments ................................................................................................ 354
 Magnetic Properties of Free Ions ................................................................................................... 359
 Orbital Contribution: Effect of Ligand-Field ................................................................................ 362
 Application of Magneto-Chemistry in Structure Determination ................................................... 370
 Magnetic Exchange Coupling and Spin State Cross Over ............................................................ 375
 Problems ........................................................................................................................................ 384
 Bibliography .................................................................................................................................. 385

CHAPTER 10 ................................................................................................................................. 386

Metal Clusters: ...................................................................................................................................... 386
 Structure and Bonding in Higher Boranes ..................................................................................... 386
 Wade’s Rules ................................................................................................................................. 401
  Carboranes ..................................................................................................................................... 407
 Metal Carbonyl Clusters- Low Nuclearity Carbonyl Clusters....................................................... 412
 Total Electron Count (TEC) .......................................................................................................... 417
 Problems ........................................................................................................................................ 424
 Bibliography .................................................................................................................................. 425

CHAPTER 11 ................................................................................................................................. 426

Metal-Π Complexes: ............................................................................................................................ 426
 Metal Carbonyls: Structure and Bonding ...................................................................................... 426
 Vibrational Spectra of Metal Carbonyls for Bonding and Structure Elucidation .......................... 439
 Important Reactions of Metal Carbonyls....................................................................................... 446

 Preparation, Bonding, Structure and Important Reactions of Transition Metal Nitrosyl, Dinitrogen
and Dioxygen Complexes.............................................................................................................. 450
 Tertiary Phosphine as Ligand ........................................................................................................ 463
 Problems ........................................................................................................................................ 469
 Bibliography .................................................................................................................................. 470

INDEX ............................................................................................................................................. 471