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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:

2 P 3/2

3 D 2

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=l 1 +l 2 , l 1 +l 2 -1, …,l 1 -l 2

(L is non negative)

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

 L: 0 1 2 3 4 5 6… S P D F G H I…

Thus, a p 2 configuration can give rise to D, P and S terms. Only electrons of unfilled shells have to be considered.

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

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

M L , which can take the values L, L-1,

Similar remarks apply to the total spin quantum number, S,

and M S , and the total angular momentum quantum number,

J, and M J .

12.2 Vector representation of total orbital angular momentum 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

For the total spin quantum number, S, (a non negative integer or half integer) the same scheme is applied:

S=s 1 +s 2 , s 1 +s 2 -1, …,s 1 -s 2

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 1s 2 ), there is no net spin, giving a singlet, 1 S. A single electron has S=s=1/2 ([Ne]3s 1 ) giving rise to a doublet term, 2 S. Likewise, [Ne] 3p 1 is a doublet, 2 P. When there are two unpaired electrons, S=1, so 2S+1=3, giving a triplet term, such as 3 D.

12.3.2 Vector representations of singlet and triplet states  12.3.1 Vector representation of total spin momentum 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 M s (M s =0) and is a singlet; the state with S=1 can have any of three values of M s (+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]3s 1 : l=0; s=1/2 therefore j=1/2. So the 2 S term has a single level, which is denoted 2 S 1/2 .

[Ne]3p 1 : l=1; s=1/2 therefore j=3/2 or 1/2. The 2 P term therefore has two levels, 2 P 1/2 and 2 P 3/2 . These levels have different energy due to the magnetic spin- orbit 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).

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 spin- orbit interaction to give J. Permitted values of J are:

J= L+S, L+S-1, …,L-S

12.5 Examples

Examples: the 3 D term of [He] 2p 1 3p 1 L=2 and S=1:

permitted values of J are 3, 2 and 1. So the term has three levels:

3 D 3

3 D 2

3 D 1

When L≥S, the multiplicity is equal to the number of levels. This is not the case when L<S: the term 2 S for example (configuration s 1 ) has only one level: 2 S 1/2 (while p 1 has two:

2 P 1/2 , 2 P 3/2 - see 12.4).

Further examples… s 2 ; s 1 s 1 ; s 1 p 1

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.

12.6 jj-coupling

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 p 2 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:

 j 1 =3/2 and j 2 =3/2 J=3, 2, 1, 0 j 1 =3/2 and j 2 =1/2 J=2, 1 j 1 =1/2 and j 2 =3/2 J=2, 1 j 1 =1/2 and j 2 =1/2 J=1, 0

12.7 Correlation diagram for two-electron systems The correlation diagram for some of the states of a two- electron system. All atoms lie between the two extremes but, the heavier the atom, the closer it lies to the pure jj-coupling case.

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 jj- coupling 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. 12.8 Selection rules
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:
3p 1 2 P 3/2  3s 1 2 S 1/2
3p 1 2 P 1/2  3s 1 2 S 1/2
By convention, the upper term precedes the lower. The
corresponding absorptions are therefore denoted:
2 P 3/2
2 S 1/2
2 P 1/2
2 S 1/2
omitting the configurations.