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Molecular Term Symbols

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in a molecule. For example,

N2 : 1g2 1u2 1u4 2g2

A given configuration may have several different states depending on how the

electrons are arranged in the valence orbital(s); a molecular term symbol labels

these states and specifies the total spin and orbital angular momentum of the

molecule, along with various other symmetries:

2S+1

(+/)

||(g/u)

S is the total spin angular momentum quantum number, formed from the

individual electrons spin quantum numbers, si = 12 , from the ClebschGordan series, as for atomic term symbols. For one unpaired electron,

S = s1 = 12 (a doublet state with 2S + 1 = 2); for two unpaired electrons

the possible values are S = s1 + s2 = 1, S = s1 + s2 1 = 0, giving triplet

(2S + 1 = 3) and singlet (2S + 1 = 1) states respectively. A closed-shell

configuration is necessarily a singlet state;

is the quantum number for the total orbital angular momentum of the

electrons about the internuclear axis. Unlike in atoms, the cylindrical

symmetry created by the strong electric field of the nuclei in a linear

L

2 ] = 0, and so L ceases to be

molecule destroys the relationship [H,

a good quantum number. Instead, we can use the quantum number ,

corresponding to the component of L along the internuclear (z-) axis:

X

=

i

i

0, 1, 2, 3, . . . is written , , , , . . .. Note that in this context, it is better

to think of the degenerate orbitals as the pair (+ , ), where the +

z =

and subscripts represent clockwise and anticlockwise rotation (L

linear combinations of the former with the same energy but they are not

z operator, so they do not contain the necessary

eigenfunctions of the L

information about ;

the g/u subscript applies only to molecules with a centre of symmetry

and labels the symmetry of the electronic wavefunction with respect to

inversion through this centre;

the +/ superscript applies only to states, and labels the symmetry of

the electronic wavefunction with respect to reflection in a plane containing

the nuclei.

For the ground state configurations of first row diatomic molecules, term symbols are deduced as follows:

Closed-shell configurations

This is the easy case; all electrons are paired off in closed orbitals, e.g.

F2 : 1g2 1u2 2g2 1u4 1g4

so there is no net orbital or spin electronic angular momentum: S = 0, = 0

and the term symbol is

1 +

g

One unpaired -electron

S = 21 , and = 0, so we have a 2 + term, e.g.

2

2

4

1

N+

2 : 1g 1u 1u 2g

2

+

g

The one unpaired electron (S = 21 ) is in a -orbital, so || = 1, and the term

symbol is 2 . For example,

2

2

1

B+

2 : 1g 1u 1u

2

O

2 ),

the configuration can be thought of as either

2 1

2 1

+ (giving = 1 1 + 1 = 1).

(giving = +1 + 1 1 = +1) or

+

1

In both cases, || = 1 and S = 2 , and the term symbol is the same as for a 1

configuration.

Two (identical) -electrons

For example, O2 , B2 . The easy way is to note that the states arising from a 2

configuration will have symmetries given by the direct product of the irreps

of the Dh molecular point group:

= + [ ]

Here, [ ] indicates the antisymmetrized product. The total electronic wavefunction, = spatial spin must be antisymmetric (electrons are fermions), so the

(spatial) part is associated with the triplet (symmetric) spin part and the

+ and parts are associated with singlet (antisymmetric) spin parts; the term

symbols are therefore:

3

, 1 + , 1

states derived from the electronic configuration. For example, the ground state

configuration of molecular oxygen is:

O2 : 1g2 1u2 2g2 1u4 1g2

Let the degenerate valence MOs be called + and corresponding to opposite

rotations of the electron around the internuclear axis. Consider the state in

which both electrons occupy + , and hence = +2:

(a)

This wavefunction is symmetric with respect to permutation of the (identical)

electrons, and so must be associated with the antisymmetric spin wavefunction.

This is the singlet state (S = 0):

1

1

spin = [(1)(2) (1)(2)]

2

The term symbol corresponding to the total wavefunction spatial spin , is therefore:

1

1

g : + (1)+ (2) [(1)(2) (1)(2)]

2

(of course, spatial = (1) (2), for which = 2, gives rise to the same term

symbol: the 1 g state is doubly degenerate).

If we place one electron in each of + and , giving = +1 1 = 0 and a

term, we must be careful to construct appropriately symmetrized spatial wavefunctions: + (1) (2) wont do because it does not have a definite symmetry

with respect to permutation of the identical electrons. We can have:

1

(b)

spatial = [+ (1) (2) + (1)+ (2)]

2

which is symmetric, and hence goes with the singlet spin wavefunction:

1

1

1

g : [+ (1) (2) + (1)+ (2)] [(1)(2) (1)(2)]

2

2

Or we can have:

1

(c)

spatial = [+ (1) (2) (1)+ (2)]

2

which is antisymmetric, and hence can go with one of the three symmetric triplet

spin wavefunctions:

(1)(2)

1

3

1 [(1)(2) + (1)(2)]

g : [+ (1) (2) (1)+ (2)]

2

2

(1)(2)

Now, the +/ superscript on these states labels the symmetry of the wavefunction with respect to reflection in any plane containing the nuclei (the operation

). Such a reflection sends a clockwise rotation to an anti-clockwise

1

(c)

spatial =

[+ (1) (2) (1)+ (2)]

2

1

= [ (1)+ (2) + (1) (2)]

2

(c)

= spatial

Similarly,

(b)

(b)

spatial = spatial

Thus, the term symbols are:

3

g ,

+

g,

reflection interchanges the degenerate + (1)+ (2) and (1) (2) functions, so degenerate

parity-conserved spatial wavefunctions, 12 [+ (1)+ (2) (1) (2)], can be

constructed. This means that the 1 g state consists of one + and one - state,

and could be written 1

g , but in practice the is usually omitted.

Spin-orbit coupling

Terms with electronic orbital angular momentum (|| > 0) and spin angular

momentum (S > 0) can undergo spin-orbit coupling; the component of the total

angular momentum along the internuclear axis, , is given as a subscript to the

term symbol. For example, the NO molecule has a 1 2 2 2 3 2 1 4 2 1 electronic

configuration and so a 2 term symbol (S = 12 and = 1). The spin angular

momentum can make a projection Sz = 12 onto the internuclear axis, and

the quantum numbers and add to give = + :

= +1 +

= +1

= 1 +

= 1

1

2

1

2

1

2

1

2

=

=

3

2

1

2

= 21

= 23

Therefore, the spin-orbit levels are = 23 and = 12 (each is doubly degenerate, since the total electronic angular momentum can be clockwise or anticlockwise about the internuclear axis); these are denoted 2 32 and 2 12 . The

splitting is about 120 cm1 , somewhat smaller than kB T at room temperature

(207 cm1 ).

Energy ordering

Hunds rules are a useful guide to the energy ordering of terms arising from the

ground state electron configuration:

1. The term with the highest spin multiplicity, 2S + 1, is lowest

in energy. This is often explained in terms of electron spin correlation:

electrons with parallel spins have a tendency to spend more time further

apart, on average, than those with paired spins.

2. For terms of the same multiplicity, the term with the largest

orbital angular momentum, given by , is lowest in energy. A

classical explanation of this says that if two electrons orbit the internuclear

axis in the same sense (say, clockwise) they will encounter each other less

often than if they orbit in opposite senses.

For example, the terms arising from the ground state of O2 lie in the order 3

g ,

1

g , 1 +

g.

Selection Rules

Electric dipole allowed transitions between electronic states of linear molecules

are subject to the following selection rules:

= 0, 1

S = 0, in the absence of spin-orbit coupling

= 0, 1

+ + ,

gu

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