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Gentry, 2012
REMINDER ON HOW TO CONSTRUCT ATOMIC TERM SYMBOLS
B) For each microstate, add each electron’s mS to get total Ms for the atom
and similarly add each electron’s ml to get Ml
For the 2p1 example:
There is only one electron for each microstate.
Therefore summing over all electrons in the microstate is a trivial exercise
Ms=Σms +½ +½ +½ -½ -½ -½
Ml= Σml -1 0 +1 -1 0 +1
H2 1σu
1s 1s
1σg
Spin:
All electrons paired, therefore # spin up equals # spin down; and MS=0
1σg (ml=0) ↑↓ (1s atomic orbitals each have ml=0)
MS = Σms 0
If MS = 0, then S=0
z-component Angular Momentum:
σ molecular orbital, therefore only ml = 0 atomic orbitals can contribute
|ML| = sum of individual ml = 0 (L=0 means s for atoms, so for molecules = Σ )
Inversion symmetry g/u
H2 has inversion symmetry, thus g/u notation is applicable
Electron #1 is in g MO, and electron #2 is in g MO, therefore g1 * g2 = g
1
Term symbol: Σg
Example 2: H2‒
MO configuration: 1σg2 1σu1
1σg2 is fully occupied so does not need to be considered
1σu1 is partially occupied with a single unpaired electron
Spin:
1σg ← Can ignore fully occupied 1σg orbital
1σu (ml =0) ↑ ↓
MS ½ -½
MS = S, S-1, ..., -S
Therefore S = ½ and spin multiplicity = 2S+1 = 2
z-component Angular Momentum:
Electron is in a σ orbital made up of 1s atomic orbitals, so ml =0 for that lone electron
Therefore |ML| = 0 (Σ)
Inversion symmetry g/u
H2- has inversion symmetry, therefore g/u is applicable
The one electron in an unfilled suborbital is in a u orbital, therefore total g/u
symmetry is u.
2
Term symbol: Σu
ml = +1
2p ml = 0
ml = -1
M s = Σ ms +1 0 0 -1 0 0
|M L| = Σ ml 0 0 0 0 -2 +2
πg2 sub-orbitals:
For O2 1π
To first approximation the two π anti-bonding MO’s are degenerate
But with spin-orbit coupling from the two electrons, there is a splitting of energies for the
different term states
πg2 Occupancy
1π
O2 2σu with spin-orbit coupling
Energy
1πg 1
Σg
1∆
g
2p 2p 3
Σg
1πu
r
2σg
1σu
2s 2s
1σg
∆|ML| = 0, ±1
Therefore Σ→Σ and Σ→Π are allowed transitions, but Σ→∆ is forbidden
∆S = 0
Change in spin multiplicity such as singlet→triplet means that an electron would have to
change the direction of its spin, and not just its orbital and energy level.
g → u,
Must change inversion symmetry between initial and final state... if inversion symmetry
exists.
Rule is a result of transition moment integral ∫ψ f µψ i dτ
µ acts like x, y, or z axis, therefore has u inversion symmetry
Only way integral can be non-zero is if overall integrand has even symmetry, g
Odd symmetry, u, would mean positive coordinates would cancel negative
coordinates
For g→u: ∫ u ⋅ u ⋅ g = ∫ g ≠ 0 but for g→g: ∫ g ⋅ u ⋅ g = ∫ u = 0
None of these selection rules are absolute, since all have built in assumptions.
But forbidden transitions are much weaker and take much longer to occur.
Because nuclei are much more massive than electrons, transitions between electronic
states occur at a much faster rate than the nuclei can respond.
Background
Ground electronic states and excited electronic states all generally follow a Morse
potential dependence of energy vs. nuclear separation distance, r.
However, the equilibrium separation distance often differs from one electronic state to
the next depending on the atomic orbitals that contribute to the specific MO.
... and the width of the potential well also differs for the two states (giving rise to
different spring constants and vibrational frequencies)
Oxygen – Bond Lengths of Molecular States
Ground State Excited State
X 3Σ g - A 3Σ u+
2σ
σ∗u 2σ
σ ∗u
Bond Order Bond Order
=2 =1
1πu 1πu
2σ
σg 2σ
σg
A molecule undergoing an electronic transition to an excited state will redistribute its nuclei
to reach its new excited-state equilibrium geometry.
But the Franck-Condon principle says that this re-positioning of nuclei is MUCH
SLOWER than the actual electronic transition between states.
Therefore the electronic transition is assumed to occur at the initial, ground-state
equilibrium position, with any re-positioning of the nuclei occurring at some later
time.
Franck-Condon Principle
1) Separation distance remains Separation distance does
constant during electronic transitions NOT change during transition
2) Later moves to new equilibrium position
2 ψf ψf
1
ψi X ψi
2
4 ψf
Absorbance ?
3
2 1 3
1
υ’=0 4
υ’=0 5
ψi 6
υ=0