12 Term symbols and selection rules

The term symbols are used to describe a certain configuration,

taking into account the subtle quantum mechanical effects
discussed earlier (lecture 11).
The convention throughout spectroscopy is to use lower-case
letters to label orbitals and upper-case letters for overall states:

12.1 The total orbital angular momentum

The total orbital angular momentum quantum number, L,

gives the magnitude of the angular momentum through
{L(L+1)}1/2

2P
3/2

3D

It gives three pieces of information:

1. The letter (P, D etc) indicates the total orbital angular
momentum quantum number, L.
2. The left superscript gives the multiplicity of the term.
3. The right subscript is the value of the total angular
momentum quantum number, J.

The value of L is obtained by coupling the individual orbital

angular momenta using the Clebsch-Gordan series:
L=l1+l2, l1+l2-1, , l1-l2

It has 2L+1 orientations distinguished by the quantum number

ML, which can take the values L, L-1,..,-L+1,-L.
Similar remarks apply to the total spin quantum number, S,
and MS, and the total angular momentum quantum number,
J, and MJ.

12.2 Vector representation of total orbital angular

momentum

(L is non negative)

For example for two p electrons, L can be 2,1 or 0.

L:

0
S

1
P

2
D

3
F

4
G

5
H

6
I

Thus, a p2 configuration can give rise to D, P and S terms.

Only electrons of unfilled shells have to be considered.

The total orbital angular momenta of a p electron and a d

electron correspond to L=3,2, and 1and reflect the different
relative orientations of the two momenta.

12.3 The multiplicity

12.3.1 Vector representation of total spin

momentum

For the total spin quantum number, S, (a non negative

integer or half integer) the same scheme is applied:
S=s1+s2, s1+s2-1, , s1-s2
Each electron has s=1/2, which gives S=1 or 0 for two
electrons. If there are three electrons, then S=3/2 or 1/2.
The multiplicity is the value of 2S+1. When S=0, (as for a
closed shell, like 1s2), there is no net spin, giving a singlet,
1S. A single electron has S=s=1/2 ([Ne]3s1) giving rise to a
doublet term, 2S. Likewise, [Ne] 3p1 is a doublet, 2P. When
there are two unpaired electrons, S=1, so 2S+1=3, giving a
triplet term, such as 3D.

12.3.2 Vector representations of singlet and triplet states

For two electrons (each of

which has s=1/2), only two
total spin states are
permitted (S=0,1). The state
with S=0 can have only one
value of Ms (Ms=0) and is a
singlet; the state with S=1
can have any of three
values of Ms (+1, 0, -1) and
is a triplet.

12.4 The total angular momentum

The total angular momentum quantum number, J, (a non
negative integer or half integer) tells the relative orientation of
the spin and the orbital angular momenta for several
electrons.
If there is a single electron outside a closed shell, J=j, with j
either l+1/2 or l-1/2.
Examples: [Ne]3s1: l=0; s=1/2 therefore j=1/2. So the 2S
term has a single level, which is denoted 2S1/2.
[Ne]3p1: l=1; s=1/2 therefore j=3/2 or 1/2. The 2P term
therefore has two levels, 2P1/2 and 2P3/2.
These levels have different energy due to the magnetic spinorbit interaction.

In case of several electrons outside a closed shell, the

coupling of all the spins and all the angular momenta has to
be considered. It can be simplified if the spin-orbit coupling is
weak (for atoms of low atomic number).

12.4.1 Summary of types of interaction resulting in a

splitting of energy levels
A summary of the types of
interaction that are
responsible for the various
kinds of splitting of energy
levels in atoms. For light
atoms, magnetic interactions
are small, but in heavy atoms
they may dominate the
electrostatic (charge-charge)
interactions.

Then the Russell-Saunders coupling scheme can be used.

All orbital angular momenta couple to give a total L, and all
spins couple to give a total S. Then they couple through spinorbit interaction to give J. Permitted values of J are:

J= L+S, L+S-1, ,L-S

12.6 jj-coupling

12.5 Examples
Examples: the 3D term of [He] 2p13p1 L=2 and S=1:
permitted values of J are 3, 2 and 1. So the term has three
levels:
3D

3D

3D

When LS, the multiplicity is equal to the number of levels.

This is not the case when L<S: the term 2S for example
(configuration s1) has only one level: 2S1/2 (while p1 has two:
2P
2
1/2 , P3/2 - see 12.4).
Further examples s2; s1s1; s1p1

Russell-Saunders coupling fails when the spin-orbit coupling is

large (in heavy atoms!). In this case the individual spin and orbital
momenta of the electrons are coupled into individual j values. Then
these momenta are combined into a grand total J. This scheme is
called jj-coupling.
Example: In a p2 configuration, the individual values of j are 3/2 and
1/2 for each electron. If spin-orbit coupling of each electron is
strong, it is best to consider each electron as a particle with angular
momentum j=3/2 or 1/2. These momenta then couple as follows:
j1=3/2
j1=3/2
j1=1/2
j1=1/2

and
and
and
and

j2=3/2
j2=1/2
j2=3/2
j2=1/2

J=3, 2, 1, 0
J=2, 1
J=2, 1
J=1, 0

12.8 Selection rules

12.7 Correlation diagram for two-electron systems

The correlation diagram for

some of the states of a twoelectron system. All atoms
lie between the two extremes
but, the heavier the atom,
the closer it lies to the pure
jj-coupling case.

Any state of the atom, and any transition, can be specified by

using term symbols.
Example: the transitions giving rise to the yellow sodium
doublet are:
3p1 2P3/2 3s1 2S1/2

3p1 2P1/2 3s1 2S1/2

By convention, the upper term precedes the lower. The

corresponding absorptions are therefore denoted:
2P
3/2

2S1/2

2P
1/2

2S1/2

omitting the configurations.

Selection rules arise from the conservation of angular momentum

during a transition and from the fact that a photon has spin 1.
They can be expressed in terms of term symbols. A detailed
analysis leads to the following rules:
DS = 0

DL = 0, 1

Dl = 1

DJ = 0, 1,
but J = 0

J=0

These selection rules apply when Russell-Saunders coupling is

valid (in light atoms).
The rules progressively fail as the atomic number increases,
because the quantum numbers S and L become ill defined as jjcoupling becomes more appropriate. For this reason, transitions
between singlet and triplet states (for which DS = 1), while
forbidden in light atoms, are allowed in heavy atoms.