H.

The full wave function of many-electron atoms. 1. Full wave function must include spin state designation. e.g., Helium, a 2 e- system

(1,2) = (1,2)( ) spatial spin part part spin wave functions are combinations of (i) or (i) which are one electron spin functions. (1,2) = (1)(2)( ) orbital 4 tentative possibilities approx for 2 spins
(1)(2) (1)(2) (2)(1)

(1)(2)

In last two combinations [(1)(2) or (2)(1)], due to the indistinguishability condition of two electrons, you have to express these as linear combinations and there are two ways to do that:

1 ((1)(2) + (1)(2)) 2 12 1 (1,2) = ((1)(2) (1)(2)) 2 12 + (1,2) =

2. So four possible spin arrangements of 2 electrons: (1)(2) (1)(2) +(1,2) (1,2)

Now comes Pauli principle: when the labels (e.g. 1 and 2) of any two identical fermions are exchanged, the total wavefunction must change sign. (antisymmetric wavefunction requirement)

(1,2) = (2,1)
If just look at spatial wavefunctions alone & if both e- in same orbital:

(1) (2) = + (2) (1)

(not antisymmetric)

Therefore the spin portion of total must be the antisymmetric part.

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Of the four possible arrangements only (1,2) is antisymmetric so:

(1,2) = (1) (2) (1,2) 1 (1) (1) (2) (2) 2 1 2 (1) (1) (2) (2)

Slater determinant

Therefore: if 2 e- in same spatial atomic orbital, only one spin state available (1,2) which is sins paired But when 2 e- are in different orbitals, all 4 of the spin combinations are possible. (1)(2) (1)(2) +(1,2) (1,2)

The first three are parallel (triplet), the last is paired (singlet) all three combos possess spin no spin angular angular momentum momentum (lower in energy) L=1 ML = -1, 0, +1 L=0

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III. Spectra of Complex Atoms. A. General. More complicated than hydrogenic spectra. Still

photon

hc = E differences between atomic energy levels

The problem is E difference between orbital energies

E.g. He He* (electronically excited Helium) 2s x 1s

2s

OR

2s

1s

1s

triplet singlet (paired spins) (parallel spins) zero total spin non-zero total spin

Difference in energy is two effects: 1. Coulombic e- -- e2. Spin correlation Triplet state is generally lower in energy than the singlet.

B.

Selection Rules for allowed transitions in many-electron atoms 1. No change of overall spin. Implies singletsinglet is allowed But singlet triplet is not allowed

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2.

Here are the allowed transitions in Helium (no singlet to triplet)

3.

Sodiums bright doublet emission:

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4.

Term symbols as labels of electronic states: e.g, what is meant by symbolism 2 P3 / 2

S, P, D gives the total orbital angular momentum L=0, 1, 2, etc Upper left superscript 2=doublet, 3=triplet gives the spin multiplicity 1=singlet,

Lower right subscript gives the total angular momentum J Optional: See text if you desire a deeper understanding.

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