Atomic term symbols


In atomic spectroscopy, the electronic state of an atom or ion can be specified by its atomic term symbol

2S+1LJ,^{2S+1}L_J,

where SS is the total spin angular momentum, LL is the total orbital angular momentum and JJ is the total angular momentum.

One method of determining all term symbols for an electron configuration is by constructing a table counting all of its possible microstates. For a given orbital quantum number ll, there is a maximum of n=2(2l+1)n=2(2l+1) orbital positions for the electrons to occupy. The total number of possible microstates NN can be calculated as a combination of all electrons occupying the available orbital positions,

N=(ne)=n!e!(ne)!,N = \left(\begin{array}{c} n \\ e \end{array}\right) = \frac{n!}{e!(n-e)!},

where nn is the number of orbital positions for a given ll and ee is the number of electrons.

For example, consider the electron configuration 2s2p22s 2p^2. The total number of possible microstates can then be calculated as

N=N2s×N2p=n2s!e2s!(n2se2s)!×n2p!e2p!(n2pe2p)!=30,N = N_{2s}\times N_{2p} = \frac{n_{2s}!}{e_{2s}!(n_{2s}-e_{2s})!} \times \frac{n_{2p}!}{e_{2p}!(n_{2p}-e_{2p})!} = 30,

where we made the substitutions n2s=2n_{2s}=2, e2s=1e_{2s}=1 to account for a single electron occupying the 2s2s orbital, and n2p=6n_{2p}=6, e2p=2e_{2p}=2 to account for two electrons occupying the 2p2p orbital. Therefore, we have 30 total microstates for the 2s2p22s 2p^2 configuration.

From the list of all possible microstates, all possible combinations of (ML,MS)(M_L, M_S) can be counted and placed in a table. The multiplet term symbol is obtained by accounting for JJ for each state. For the example of 2s2p22s 2p^2, we have:

MLMS321212322011011331014411133120110M_L \begin{array}{c|cccc} & &M_S & & \\ & -\frac{3}{2} & -\frac{1}{2} & \frac{1}{2} & \frac{3}{2} \\ \hline -2 & 0 & 1 & 1 & 0 \\ -1 & 1 & 3 & 3 & 1 \\ 0 & 1 & 4 & 4 & 1 \\ 1 & 1 & 3 & 3 & 1 \\ 2 & 0 & 1 & 1 & 0 \end{array}

We can then start extracting terms from this table, starting from the top-left corner to the bottom-right. From the top row, we can extract the term 2D^2D for ML=2|M_L| = 2 and multiplicity 2: one with MS=1/2M_S = -1/2 and one with MS=1/2M_S=1/2. Accounting for JJ, we obtain 2D3/2,5/2^2D_{3/2,\,5/2}. When subtracting, we remove 1 from the entire column. The resulting table is then:

MLMS32121232112210133111221M_L \begin{array}{c|cccc} & &M_S & & \\ & -\frac{3}{2} & -\frac{1}{2} & \frac{1}{2} & \frac{3}{2} \\ \hline -1 & 1 & 2 & 2 & 1 \\ 0 & 1 & 3 & 3 & 1 \\ 1 & 1 & 2 & 2 & 1 \end{array}

where we have removed the ML=2M_L = -2 and ML=2M_L = 2 rows since they now contain all 0s. In the next step, we can extract the term 4P^4P for ML=1|M_L| = 1 and multiplicity 4: one each with MS=3/2,1/2,1/2,3/2M_S = -3/2, -1/2 , 1/2, 3/2. Accounting for JJ, we obtain 4P1/2,3/2,5/2^4P_{1/2,\,3/2,\,5/2}. The resulting table is:

MLMS32121232101100022010110M_L \begin{array}{c|cccc} & &M_S & & \\ & -\frac{3}{2} & -\frac{1}{2} & \frac{1}{2} & \frac{3}{2} \\ \hline -1 & 0 & 1 & 1 & 0 \\ 0 & 0 & 2 & 2 & 0 \\ 1 & 0 & 1 & 1 & 0 \end{array}

Here we can extract the term 2P^2P for ML=1|M_L| = 1 and multiplicity 2: one each with MS=1/2,1/2M_S = -1/2, 1/2. Accounting for JJ, we obtain 2P1/2,3/2^2P_{1/2,\,3/2}. The resulting table is:

MLMS3212123200110M_L \begin{array}{c|cccc} & &M_S & & \\ & -\frac{3}{2} & -\frac{1}{2} & \frac{1}{2} & \frac{3}{2} \\ \hline 0 & 0 & 1 & 1 & 0 \\ \end{array}

where we have removed the ML=1M_L = -1 and ML=1M_L = 1 rows since they now contain all 0s. We are left with the final row, which we can extract the term 2S^2S for ML=0|M_L| = 0 and multiplicity 2: one each with MS=1/2,1/2M_S = -1/2, 1/2. Accounting for JJ, we obtain 2S1/2^2S_{1/2}.

Therefore for the 2s2p22s 2p^2 configuration, we have obtained the following 8 terms:

2D3/2,5/2,4P1/2,3/2,5/2,2P1/2,3/2,2S1/2{}^2D_{3/2,\,5/2}, {}^4P_{1/2,\,3/2,\,5/2}, {}^2P_{1/2,\,3/2}, {}^2S_{1/2}

I have written a python script to calculate atomic term symbols based on this method here.