Transition Moments

Quantitative Calculations of Spectroscopic

Transitions

Analogous to Section 13-12

Selection Rules – Calculation of electric dipole transition moments
We have already encountered a symmetry-based selection rule for simple
absorption and emission:
g ↔ u, g ←/→ g, etc..
We have also seen how symmetry rules allow one to extend this concept.
Light incident on a molecule will interact via a vector, E, describing the
amplitude of the electric field.
E = E0 cos (ωt) = E0 cos (2πνt) (Eq. 13.40)
This electric field will induce a fluctuating dipole moment in the molecule by
displacing the centers of positive and negative charge at the frequency of the
field. If the frequency is resonant with a pair of energy levels then
absorption may be able to occur.
If the molecule is randomly oriented in space, the electric vector will have
components along the x, y and z axes of the molecule. Thus, the symmetry
classification of the electric dipole operator for an absorption or emission
event would
12/5/2016 be the same as one of transition
Electronic the Cartesian
momentsaxes. 2
If a function having even symmetry is operated on by an operator having odd
symmetry, the result must be odd:
g × u = u , etc.
Perturbation theory allows us to write the integral describing the electric dipole
transition moment between two states of a molecule according to:

µ fi = e ∫ ψ f * qψ i dτ

Here ψi is the ground state and ψf is the excited state. The

quantity q is a displacement vector for electric charge and e is the charge
on the electron. We could also write: qe = µ, which is a dipole moment
operator. Note that “μ” is not usually the permanent dipole moment, but
is an induced dipole. (Pure rotational transitions do involve the
permanent dipole moment).
In a molecular frame of reference, we could replace q by x, y, or z.
Let’s see
12/5/2016 a quantitative example of how
Electronic this moments
transition works. 3
 Example of the Application of Time Dependent Perturbation Theory

Transition Moment Matrix Element for 2px ← 1s of the H atom

We need to calculate the integral representing the transition:

µ (2p x ← 1s ) = e ∫ ψ *2 p xψ 1s dτ
x
(See Eq. 13.54)

for which we need the normalized hydrogen-atom wavefunctions:

1 − r / a0 1 − r / 2 a0
ψ 1s = e ; ψ2p = 5
r sin θ cos φ e
π a0 3 x
32π a0

In polar coordinates, the x vector is expressed as:

x = r cos θ sin φ Don’t forget the
terms at the end:
This gives for the full integral:
Electron charge
1 1
µ (2p x ← 1s ) = e ∫ r sin θ cos φ e − r / 2 a0
r cos θ sin φ e − r / a0
r 2
dr sin θ dθ dφ
32π a0 π a0
5 3

12/5/2016 ψ2px Electronic transition moments ψ1s 4

Splitting this up and then applying standard integrals, we have:

∞ π 2π
e 256 a0e
4 ∫ ∫ ∫ φ dφ =
4 −3 r / 2 a0
µ (2p x ← 1s ) = r e dr sin 3
dθ cos 2
= 0.745a0 e
4 2 π a0 0 0 0
243 2

12/5/2016 Electronic transition moments 5

Or let MathCad do it:

On this first page, we input

some wave functions,
including translating x, y
and z to polar coordinates.

12/5/2016 Electronic transition moments 6

 Integrals are the reverse of:

Δℓ=±1 Lyman α

Wrong polarization

Δℓ=±1 Lyman α

Δℓ=±1 Lyman β

Δℓ=±1 Balmer α

Note that in H, the 3s

and 3p orbitals have
the same energy.
12/5/2016 Electronic transition moments 7
 The units for the transition moment as calculated are in units of a0e, which
are the dimensions of a dipole moment. Since a0 = 5.292 × 10-11 m and
e = 1.602 × 10-19 C, the quantity a0e = 8.478 x 10-30 C.m = 2.54 D. (1D = 3.336 x 10-30
C.m). We can evaluate: µ(2p ← 1s) = 0.745 × 8.478 x 10-30 = 6.32 x 10-30 C.m.
What is the significance of this result? The value of the transition moment,
0.745 a0e, implies that an electron has been displaced (on average) through 0.745
times the Bohr radius. This is a direct measure of the strength of the transition
moment.
Physically, we have converted the wave function from a spherical form to
the form of a p-orbital. This rearrangement of charge induced by the electric field
is responsible for the transition dipole moment. Note that there is no permanent
dipole moment in either case.
Other results shown indicate that the transition moment integral varies
significantly depending on the wavefunctions involved. The strength of the
transition is proportional to the square (strictly the modulus squared) of the
transition moment integral. 8