A deeper look 5 Rotational selection rules

The starting point for the identification of rotational selec-

μz
tion rules is the general definition of the transition dipole
μ0
moment between states with wavefunctions ψi and ψf:
θ

µ fi = ∫ψ f* µˆψ idτ
μx μy
ϕ
where µ̂
µ is the electric dipole moment operator, −er.
Figure 1 The relation between the three components of the
(a) Pure rotational selection rules dipole moment and the angles θ and ϕ.

The procedure involves expressing trigonometric func-

tions and the rotational wavefunctions in terms of spheri- Step 3 Evaluate the integral using a standard result
cal harmonics (Table 7F.1) and then using standard With these substitutions, the transition moment becomes
integrals to identify the criteria for the integrals to be a sum of terms each of which is an integral over the prod-
non-zero. uct of three spherical harmonics of the form
Step 1 Identify the rotational wavefunctions
For a diatomic molecule the rotational wavefunctions are
∫Y *
Jf , M J, f Yj, mYJ , M dτ r
i J, i

the spherical harmonics YJ, M (θ , φ ) (Topic 7F). The transi- J

with j = 1 and m = 0, ±1, depending on which component
tion dipole moment for the spectroscopic transition f ← i
is involved. This integral is well known in the theory of
is therefore
angular momentum and is zero unless MJ,f = MJ,i + m
and Jf = Ji ± j. Because m = 0, ±1 it follows that ΔM =
µ fi = ∫ψ ε*ψ v*YJ*, M µˆψε ψv YJ , M dτ
f f f J ,f i i i J ,i
MJ,f − MJ,i = 0 or ±1, and because j = 1 it follows that ΔJ =
Jf − Ji = ±1.
For a pure rotational transition the initial and final
electronic and vibrational states are the same, and so
µ i = ∫ψ ε*ψ v* µˆψ ε ψ v dτ e,v can be identified as the permanent
i i i i
(b) Rotational Raman selection rules
electric dipole moment of the molecule in the state i. This Consider a diatomic molecule, with polarizabilities α||
equation then becomes and α⊥, and an electric field E applied in the laboratory
Z-direction. The induced dipole moment is parallel to the
µ fi = ∫ YJ*, M µ iYJ , M dτ r
f J, f i J, i Z-axis, so µZ = αZZE.
Step 1 Express the component in the molecular frame
The remaining integration, denoted dτr, is over the rota-
tional coordinates of the molecule. It follows immediately In the molecular frame, the components of the dipole
that the molecule must have a permanent dipole moment moment are µx, µy, and µz, and from Fig. 2 it follows that
in order to have a microwave spectrum: this is the gross
selection rule for microwave spectroscopy. µZ = µx sinθ cosφ + µ y sinθ sinφ + µz cosθ
Step 2 Write the dipole moment in terms of spherical
harmonics
z Z
The three components of the dipole moment can be writ-
ten in terms of the angles θ and ϕ (Fig. 1) θ
x

µi,x = µ0 sinθ cosφ

y
µi, y = µ0 sinθ sinφ ϕ

Y
µi,z = µ0 cosθ
X

These trigonometric factors can be written in terms of the

three spherical harmonics Y1,0 , Y1,±1 listed in Table 7F.1:
Figure 2 The components of the dipole moment µx, µy, and
µi,x ∝ µ0 (Y1,1 − Y1,−1 ) µi , y ∝ µ0 (Y1,1 + Y1,−1 ) µi ,z ∝ µ0Y1,0 µz, in relation to the laboratory frame.
2 A deeper look 5 Rotational selec tion rules

Similarly, the components of the electric field are Now note from Table 7F.1 that
E x = E sinθ cosφ E y = E sinθ sinφ E z = E cosθ  5 
1/2

Y2,0 (θ ,φ ) =  (3cos 2 θ −1)

 16π 
Step 2 Express the induced components of the dipole
moment in the molecular frame so
Because the component of the induced electric dipole 1/2
 π 
moment in the molecular frame, q = x, y, z, is related to cos 2 θ = 13 1+ 4   Y2,0 (θ ,φ ) 
  5  
the component of the electric field in that frame by µq =
αqqE q, it follows that
It then follows that
α⊥ α⊥ α ||
    π
1/2

µZ = α xx E x sinθ cosφ + α yy E y sinθ sinφ + α zz E z cosθ µZ = α + 43   ∆α Y2,0 (θ ,φ ) E
 5 
 
= α ⊥E sin 2 θ cos 2 φ + α ⊥E sin 2 θ sin 2 φ + α E cos 2 θ

cos2 x + sin2 x = 1, x = ϕ
Step 4 Evaluate the transition dipole moment
Finally, consider the integral that defines the transition
= α ⊥E sin 2 θ + α E cos 2 θ moment:
cos2 x + sin2 x = 1, x = θ
µfi = ∫ YJ*, M µZYJ , M dτ r
f J, f i J, i

= α ⊥E + (α  − α ⊥ )E cos θ 2
1/2
 π
= α E ∫ YJ*, M YJ , M dτ r + 43   ∆α E ∫ YJ*, M Y2,0YJ , M dτ r
f J, f i
 5
J, i f J ,f i J ,i

Step 3 Express the angles in terms of spherical harmonics

The first term is zero if Jf ≠ Ji and MJ,f ≠ MJ,i and so does not
The mean polarizability is defined as
contribute any off-diagonal elements: it is responsible for
α = 13 (α  + 2α ⊥ ) the unshifted Rayleigh line. The second term gives a contri-
The anisotropy of the polarizability is defined as bution only if both ∆α and the integral do not disappear.
The former requirement implies that the polarizability must
∆α = α  − α ⊥ be anisotropic; the latter requires Jf = Ji ± 2 and MJ,f = MJ,i.