Indian Institute of Technology, Guwahati

Guwahati, INDIA 781 039

Department of Chemistry Date: October 2010

CH101
Class 9; Physical Chemistry
Spectroscopic Transitions and Selection Rules

The energies of hydrogenic atoms are given by

Z 2 µe 4
En = −
32π 2ε 02 2 2
n
Also, you have so far learned that the transition energies (between two states) can be
expressed by
1 1 µ H e4
∆E = En1 − En2 = RH ( − ) = hcR H =
n22 n12 32π 2ε 02 2

Now consider the electron to be in an orbital n1, l1, ml1 (lower energy) and makes a
transition to another orbital with quantum numbers n2, l2, ml2. This transition has
occurred due to absorption of a photon with frequency ν and energy hν.

That is ∆E = hυ

Is it possible to have transitions from any arbitrary state another arbitrary state? NO!

Selection Rules Decide:

Photon has an intrinsic spin angular momentum of 1. The change in the angular
momentum of electron must consider the angular momentum of the photon which the
electron absorbs or emits.

In general : s-orbital (l=0) to d-orbital (l=2) transition is forbidden for a single photon
transition.

Similarly : s-orbital (l=0) to s-orbital (l=0) transition is forbidden for a single photon
transition.

How to decide? Evaluate the transition dipole moment, µf,I; where µ is the electric
dipole moment operator. For one-electron atom µ=-er. The components are µx=-ex; µy=-
ey and µz=-ez.

It the transition dipole moment is zero then the transition is forbidden and if the transition
dipole moment is non-zero then the transition is allowed.

1
To evaluate a transition dipole moment one evaluates each component in turn. For
example, for the z-component

µ f ,i = −e f z i = −e Ψ *f zΨi dτ

We already know that

5/2
1 Z
Ψ p 0 = R 2 ,1 ( r )Y1, 0 (θ , ϕ ) = r cos θ e − Zr / 2 a 0
4 ( 2π ) 1/ 2
a0
= r cos θ f ( r )
1/ 2
3
Ψ p z = zf ( r ); and : Y1 , 0 = cos θ ;
4π
1/ 2
4π
∴z= rY 1, 0
3
Then
1/ 2
4π ∞ π 2π
Ψ zΨi dτ =
*
f Rn f ,l f rRni ,li r 2 dr Yl*f ,ml , f Y1, 0Yli ,mi sin θdθdϕ
3 0 0 0

It is known from the properties of the spherical harmonics that the integral
π 2π
Yl*f ,ml , f Y1, 0Yli ,mi sin θdθdϕ
0 0
is zero unless lf = li ± 1 and ml,f = ml,i ± m.

In the present case m = 0; the angular integral and hence the z-component of the
transition dipole moment is zero unless ∆l = ±1; and : ∆ml = 0 . This is the part of
the selection rules. The consideration of the x and y components would results into the
complete set of selection rules.

2
Many-electron Atoms
Wavefunction of a many-electron atom can be described by Ψ ( r1 , r2 , r3 ...) ; where r1,
r2, r3… are the vectors of separation between the nucleus and the electron in point.

In orbital approximation: Ψ (r1 , r2 , r3 ...) = Ψ (r1 )Ψ (r2 )Ψ (r3 )...

Here each individual orbital resembles that of Hydrogenic orbitals, with the effective
nuclear charge modified by the presence of other electrons.
Consider the case of Helium that has two electrons. Assume that there is no interaction
between the electrons. One can write the Hamiltonian as H = H1 + H2.

HΨ (r1 , r2 ) = HΨ (r1 )Ψ (r2 ) = ( H1 + H 2)Ψ (r1 )Ψ (r2 )

= H1Ψ (r1 )Ψ (r2 ) + H 2Ψ (r1 )Ψ (r2 ) = ( E1 + E 2 )Ψ (r1 )Ψ (r2 ) = EΨ (r1 )Ψ (r2 )

However, if there is interaction between the electrons the above proof is not valid.
One has to consider the spins of electrons also.
Pauli Exclusion Principle: General statement:
When the levels of any two identical fermions (particles with half-integer spins) are
exchanged, the total wavefunction changes sign. When the levels of any two identical
bosons (particles with integer spins) are exchanged, the total wavefunction retains the
same sign.
Consider the wavefunction for a two-electron system: Ψ (1,2) . It can be considered to

be made up of two wavefunctions Ψ (1) and Ψ (2) . Consider also the spins of the

electrons: α and β.
There are four possible wavefunctions that can be generated form these.

Ψ (1)Ψ (2)α (1)α (2)

Ψ (1)Ψ (2) β (1) β (2)
1
Ψ (1)Ψ (2)[ {α (1) β (2) + β (1)α (2)}]
2
and
1
Ψ (1)Ψ (2)[ {α (1) β (2) − β (1)α (2)}]
2

3
Consider the following: Electrons are fermions and their combined wavefunction must
change its sign once the electrons are interchanged. In other words,
Ψ (1,2) = −Ψ (2,1)
Of the four wavefunction mentioned above only the last one changes its sign upon
interchange of electrons. Thus the last one is the spin-considered a valid complete
wavefunction for a two-electron system.

1 1
Ψ (1)Ψ (2)[ {α (1) β (2) − β (1)α (2)}] = −Ψ (2)Ψ (1)[ {α (2) β (1) − β (2)α (1)}]
2 2

Hund’s rule of Maximum Multiplicity:

An atom in its ground state adopts a configuration with the greatest number of
unpaired electrons.

Suppose electron 1 is described by a wavefunction Ψa (r1 ) and electron 2 is described

by a wavefunction Ψb (r2 ) . Then the simplest and combined expression for the

wavefunction of the two electons is Ψ = Ψa (r1 )Ψb (r2 ) . This is not, however,

acceptable. As this means we know beforehand which electron is in which orbital. This
is not possible as electrons are indistinguishable.
We can describe the two-electron wavefunction by either of the following two functions
1
Ψ+ = [ { Ψ a ( r1 ) Ψ b ( r2 ) + Ψ b ( r1 ) Ψ a ( r2 )}]
2
or
1
Ψ− = [ { Ψ a ( r1 ) Ψ b ( r2 ) − Ψ b ( r1 ) Ψ a ( r2 )}]
2

According to Pauli exclusion principle, as is Ψ+ symmetric, it must be multiplied by a

1
spin wavefunction that is antisymmetric. This is [ {α (1) β (2) − β (1)α (2)}] .
2

4
 1
This configuration Ψ+ [ {α (1) β (2) − β (1)α (2)}] corresponds to a spin-paired
2
state. On the other hand

According to Pauli exclusion principle, as is Ψ− antisymmetric, it must be multiplied by

a spin wavefunction that is symmetric. This could be one of the following three spin
states:
α (1)α (2)
α
β (1) β (2)
1
[ {α (1) β (2) + β (1)α (2)}]
2
β

These symmetric spin-states corresponds to electrons with parallel spins.

Now consider the spatial wavefunctions Ψ+ and Ψ− .

1
Ψ+ = [ {Ψa (r1 )Ψb (r2 ) + Ψb (r1 )Ψa (r2 )}]
2
or
1
Ψ− = [ {Ψa (r1 )Ψb (r2 ) − Ψb (r1 )Ψa (r2 )}]
2

When one sets r1=r2, then Ψ− becomes zero. This means that the probability of finding
two electrons in the same point in space is zero when they have parallel spins. Thus the
right configuration is the anti-parallel spins (Hund’s rule).