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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.

The 'definition' of the term symbol:

LJ

2S+1

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|

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

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.

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!

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.

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)

{ There is neither a

S0

nor a

S-1

Term }

B (1s22s22p1)

{ground state}

P1/2

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

3

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

Assign Terms

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:

the states arising from a given electronic configuration, you

should try Ti(1s22s22p63s23p64s23d2)

Here is the answer depicted graphically

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