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Atomic Term Symbols

The Stationary States of the Many-Electron Atom are


determined by the overall properties of the Atom, not those of
the individual electrons that exist in the atom.
What are these overall properties?
The total orbital angular momentum of the electrons, L
The total spin angular momentum of the electrons, S
The total angular momentum of the atom, J
Thus, the eigenstates of the Hamiltonian for the atom are
labeled by these properties. These labels are called
Atomic Term Symbols.

Atomic Term Symbols


The 'definition' of the term symbol:

LJ

2S+1

Note: In the symbol L must be replaced with its alphabetic 'code':

L=0 is S,
L=1 is P,
L=2 is D,
L=3 is F,
L=4 is G,
L=5 is H...
J is the vector sum of L and S:
J = (L+S), (L+S-1), (L+S-2), ....|L-S|

Assigning Term Symbols:


The ground state of hydrogen atom is one electron in the lowest
energy atomic orbital: the 1s.
Therefore the total orbital angular momentum of all (one) electrons
is L=l=0, and the total electron spin is S=s=1/2.
Applying the 'definition' of the term symbol results in a 2S1/2 atomic
term for the ground state of the H atom.
This symbol is read: doublet Ess one half

Exciting the single hydrogenic electron to higher orbitals results in


different atomic states or 'terms' of the atom. Note that an H atom
with the electron in a 3d and 10d orbital both result in 2D3/2 and 2D5/2
terms, but at different energies.

The lowest electron configuration of He is 1s2. The ground state of the


neutral helium atom is therefore 1S0 since the total orbital and spin
angular momentum of this configuration is zero.
In fact, any electron configuration (orbital population) that consists of any
combination of closed shells or subshells will result in this (totally
symmetric 1S0 term.
Therefore, in the designation of atomic terms, the contribution from
closed subshell electrons may be neglected.
What cant be neglected? The resultant angular momenta of the
open-shell electrons in the atom!

Because the angular momenta of each electron adds to the rest of


the electrons vectorially, there will, in general, be more than one
possible result of this addition. It is our job to account for each and
every possible way in which the properties of the electrons will sum
up and sort those possibilities into those corresponding to distinct
Terms (total energies; atomic eigenstates).
We will seek to categorize each the ways in which the electrons
add up by a complete description of the l, ml, ms (s is the same for
all e-s ) of each electron: This is called a microstate. A given
microstate is not necessarily a good description of the state of the
entire atom; sometimes many microstates are needed to describe
a given Term.

To determine the states (Terms) of a given Atom or Ion:


1. Write down the electronic configuration (ignore closed subshell
electrons)
2. Determine the number of distinct microstates that can represent
that configuration. If you have e electrons in a single open subshell of
2l+1 orbitals, this value is
#microstates(single open subshell) = (2(2l+1))!/e!(2(2l+1)-e)!
3. Tabulate the number of microstates that have a given ML and MS
4. Decompose your table into terms by elimination
5. Test the total degeneracy of the resultant terms to account for all
the microstates counted in parts 2 and 3
6. Determine the lowest term for the configuration by Hunds Rules.

Summary Examples
H (1s1)
ground state term symbol is 2S1/2
He (1s2)
Ground state term symbol is 1S0

He (1s12s1)

An Excited State Configuration

Terms: 1S0 , 3S1


{ There is neither a

S0

nor a

S-1

Term }

B (1s22s22p1)

{ground state}

Term symbol: 2P1/2, 2P3/2

The spin orbit splitting is regular so

P1/2

is the ground state.

2 2 2
C (1s 2s 2p ) {lowest electron configuration}
Calculate the number of possible electron arrangements
in the given configuration:
There are 6!/4!2! = 15 microstates expected

Write down all these possibilities :

Tabulate the total numbers by ML and MS

Decompose this table into terms

Check with reality:

3
N (1s 2s 2p ) {lowest energy configuration}

This configuration has 6!/3!3! = 20 microstates

Draw all the possibilities

Tabulate the totals

Assign Terms

Check with reality

What are the atomic state term symbols resulting from


the lowest energy configuration of O (1s2 2s2 2p4) ?
Aha! We don't haver to do this because the terms
arising from p2 and p4 are exactly the same!
Note, however, the ordering of the J levels is now
inverted

Reality:

If you think you have mastered the process of determining


the states arising from a given electronic configuration, you
should try Ti(1s22s22p63s23p64s23d2)
Here is the answer depicted graphically

Some results of this procedure for your amusement: