1.

Term symbols for diatomic molecules

 Term symbols characterize key features of electron spin and
orbital angular momentum 2S 1
L
For an atom: J

Important terms 2S
For a diatomic: 1
→  
 projection of orbital angular momentum onto the internuclear axis.
 
Magnitude: | | ħ
L 1 2
Symbols: Λ 0 1 2 Atoms
P D
Symbol Σ Π ∆
0
S total electronic spin angular momentum (the sum of electron spin inSunfilled shells)
Symbol
Magnitude: | S 
| Sħ , S will have 1/2-integer values
projection of S onto the internuclear axis (only defined when Λ ≠
 0).
Magnitude: | |  ħ
2S 1
Allowed values:   S , S  1,...,S
valuesaxis of electron spin and orbital
 sum of projections along the internuclear angular
momentum
 +
    S,   S 1,...,   2S 1 values for  
1
S S
 1. Term symbols for diatomic molecules
 Examples
NO The ground state for NO is X2Π For a diatomic:
2S
1 
S = 1/2, Λ = 1, Ω = 3/2, 1/2
There are two spin-split sub-states: 2Π1/2, 2Π3/2
Separation: 121cm-1

CO The ground state for CO is X1Σ+

S = 0 and Λ = 0, therefore Ω is unnecessary. This is a rigid rotor
molecule. Easiest case!

O2 The ground state for O2 is X3Σg –

S = 1, Λ = 0
The – and g are notations about symmetry properties of wave
functions. This is an example of a molecule that is modeled by
Hund’s case b

2
 2. Common molecular models for diatomics
 Four common molecular models

Rigid Rotor Λ = 0, S = 0 2S+1 = 1  “singlets”

no influence of electron spin
Symmetric Λ ≠ 0, S = on spectra
Top 0 Λ ≠ 0, S Spin important through
Hund’s a ≠ 0 Λ = 0, interaction of Λ and Σ
Hund’s b S≠0

 This lecture:
Rigid Rotor
Symmetric Top
Followed by:
Hund’s a
Hund’s b

3
3. Electronic Spectra of Diatomic Molecules:
Improved Treatments (add Spin)

Hund’s case a
1. Review of angular momentum
2. Interaction of Λ and Σ
3. Hund’s case a (Λ≠ 0, S ≠ 0)
4. Hund’s case b (Λ = 0, S ≠ 0) Hund’s case b
5. Λ-doubling

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 3.1. Review of angular momentum
 Review – then add spin
 Term symbol
“Multiplicity” of state

Term Symbol 2 S 1 Sum of projections on A axis


Λ 0 1 2 Projection of electron
when Λ ≠ 0
Symbol Σ Π orbital angular 
momentum on A     S,   S 1,...,  
∆ axis S

 Rigid Rotor
4 models Λ=S=0 e.g., N2, H2: X1Σ
 Symmetric Top Λ ≠ 0; S = 0 e.g., 1Π
 Hund’s a Λ ≠ 0; S ≠ 0 e.g., OH, NO (both X2Π)
Add spin
 Hund’s b Λ = 0; S ≠ 0 e.g., O2: X3Σ

5
 3.1. Review of angular momentum
  Electronic angular momentum for molecules
 Orbital angular momentum of electrons
1. Separate from spin and nuclear rotation

2. Strong electrostatic field exists between nuclei.

So precesses about field direction (internuclear axis) with “allowed”
components along axis
→
 
L
ml = L, L-1, …, -L ≡ Λ

3. If we reverse direction of electron orbit in field, we get the same

energy but Λ → –Λ (Λ doubling)

6
 3.1. Review of angular momentum
 Electronic angular momentum for molecules
 Spin of electrons
1. To determine L and S for molecule, we usually sum l & s for all

electrons. e.g., S   si
i
So even number of electrons  integral
spinodd number of electrons  half-integral spin

2. For Λ ≠ 0, precession of L about internuclear axis  magnetic field

along axis. So ms is defined. ms ≡ Σ = S, S-1, … -S.

Note for change of orbital direction, energy of electron spinning in

magnetic field changes  no degeneracy  2S+1 possibilities
(multiplets)

3. For Λ = 0, no magnetic field exists and the projection of S on the

nuclear axis is not conserved (Σ not defined)

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 3.1. Review of angular momentum

  Electronic angular momentum for molecules
 Total electronic angular momentum
1. Total electronic angular momentum along internuclear axis is + But
since all in same direction, use simple addition



2. For Λ ≠ 0, magnetic field H ∝ Λ.

Magnetic moment of “spinning” electron μH ∝ Σ.

So interaction energy is proportional to E ~ μH ~ ΛΣ, or

Te = T0 + AΛΣ (more on this later)

For A > 0, “Regular” state

For A < 0, “Inverted” state

2
 2

1/ 2 8
3/ 2
 3.2. Interaction of Λ and Σ
 This interaction is key to modeling the influence of spin on the
electronic state structure.
N J
Nuclear Rotation

   

When Λ ≠ 0, S ≠ 0, they combine to form a net component

of Ω.

Λ ≠ 0  an associated magnetic field due to net current about

the axis. This field interacts with spinning electrons.

 Spin-orbit coupling (spin-splitting of energy levels)

Comments:
 Models are only approximations.
 Coupling may change as J ranges from low to high 9
values
 3.2. Interaction of Λ and Σ
 Examples 3 ∆3 ← S = 1, Λ = 2, Ω = 3 (Σ = 1)
3 ∆ ← S = 1, Λ = 2, Ω = 2 (Σ = 0)
3∆ 2
3 ∆ ← S = 1, Λ = 2, Ω = 1 (Σ = –1)
1

Electronic energies Te  T0  A

Spin-orbit coupling constant, generally
Energy without increases with molecular weight and
interaction the number of electrons
3 ∆  S = 1, Λ = 2, Σ = 1,0,–1
3∆
1 
 2A
3
3∆ For A>0
Te  T0  A2 0 3∆
2

 1  3∆ 1

 Notes:
ABeH ≈ 2 cm-1
ANO ≈ 124 cm-1 1. The parameter Y is often specified,
Sample constants
AHgH ≈ 3600 cm-1 where Y = A/Bv
AOH ≈ -140 cm-1 Negative! 2. Values for A given in Herzberg,
Vol.I 10
Now, consider Hund’s cases where S ≠ 0
 3.3. Hund’s case a
 Λ ≠ 0, S ≠ 0, Σ = S, S-1, …, -S

F J   BJ J 1 A  B  2  Recall
h h
    S,   S 1,...,   S ,B
8 I A c 
2
8 2 I B c
J  , 
A Not to be confused
1,... with spin-orbit constant
P, Q, R branches for each value of Ω.

Example:
2 Π  Ω = 3/2 and 1/2, two electronic sub-states

 a total of 2 x 3 = 6 branches

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 3.4. Hund’s case b
 Applies when spin is not coupled to the A-axis
 E.g., 1.
  For Λ = 0, is not defined, must use

2. At high J, especially for hydrides, even with Λ ≠ 0

→
→ 𝐽 
N 

→
s 

Allowed
  J: J = N+S, N+S-1, …, N-S, J ≥ 0 only

For this case, and couple directly,

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 3.4. Hund’s case b
 Example – O2
 Ground state X3Σ has three J’s for each N!
F1(N) F2(N) F3(N)
J=N+1 J=N J=N–1

J=3  Notes:
N=2  Split rotational levels for N > 0
J=2
J=1  Each level has a degeneracy
J=2 of 2J + 1, and a sum of
N =1 Hönl- London factors of 2J +
J=1 1
 Minimum J is |N-S|
J=0
 In N = 0 level, only spin is
J=1 active (S = 1), this is the
N =0 minimum value of J
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 3.5. Λ – doubling
 Further complexity in the energy levels resulting from Λ-doubling
  
 Different coupling with nuclear rotation ( and
interaction)

 The two orientations of (± Λ along the A-axis) have slightly

different energies
F J   Fc J and Fd J 
Fc(J)
F(J)

Fd(J)

 By definition, Fc(J)>Fd(J) (c,d replaced by e,f in some literature)

 Lambda doubling usually results in a very small change in energy,
affecting Boltzmann distribution only slightly.
 Change of parity between Λ-doubled states – reduces the accessible
fraction of molecules for a given transition (due to selection rules)
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