Rotational-vibrational spectra

The oscillating rotator

For a diatomic molecule, which we treat as a rigid rotator with a bond length fixed in the
equilibrium position, the moment of inertia is Ie = µre2. Here, µ is the reduced mass.

In the case of a rotator in vibrational motion, re needs to be replaced by the average of the square
of the the internuclear distance. Consequently, the moment of inertia becomes Iv = µ< r2>.
Explicitly calculated with r = re ±s:

Iv = µ<r2> = µ<(re ± s)2> = µre2± 2<µsre> + µ<s2> = µre2 + µ<s2>

Within one oscillation, the addend 2<µsre> is compensated to zero. The third addend and the
moment of inertia Iv remain for a molecule which has a vibration larger than µre2. In turn, the
rotational constant B becomes dependent on the vibrational state. Note that Bv < Be

with vibration: without vibration

Bv = h/4πcµrv2 Be = h/4πcµre2.

Besides the approach from classical physics, the problem has as well been treated with purely
mathematical means. A result of this is the following equation that represents a first
approximation using a small correction coefficient αe to quantify the influence of the vibrational
states v on the rotational constant Bv.

Bv = Be - αe(v + ½)

Example HCl: αe = 0.3072

Be Bv = 0 Bv = 1 Bv = 2 Bv = 3
10.5934 cm-1 10.44 cm-1 10.13 cm-1 9.83 cm-1 9.52 cm-1

In addition to the influence of the molecule's oscillations, rotation itself affects molecular
constants, i.e., centrifugation will stretch bonds (compare chapter Elastic rotor). The centrifugal
stretching constant D introduces this phenomenon into our mathematical description of
molecular energy levels. Note that, like B, constant D is function of the vibrational state and the
correction coefficient βe quantifies the respective dependency.

Dv = De - βe(v + ½)
 Example HCl: βe = 7.51⋅10-6
De Dv = 0 Dv = 1 Dv = 2 Dv = 3
5.32⋅10-4 cm-1 5.28⋅10-4 cm-1 5.21⋅10-4 cm-1 5.13⋅10-4 cm-1 5.05⋅10-4 cm-1

First, we ignore the orientation of electron orbitals respective to the molecule's axis and expect
the energies of rovibrational states to be the sum the following main ? addends.

E = Evib + Erot = ωe(v + ½) - ωexe(v + ½)2 + BvJ(J + 1) - DvJ2(J + 1)2

We further ignore centrifugal stretching and keep on treating the possible rotational states J as a
parameter. Then, the energy differences for transitions v' ← v with v' = v + 1 become:

ΔE = ωe - 2ωexe(v + 1) + {Bv'J'(J' + 1) - BvJ(J + 1)}

= ν0

For ΔJ = + 1 or J + 1 ← J, we speak of absorption peaks within the so-called R-branch. Their

wavenumbers ν are

ν = ν0 + 2Bv' + (3Bv' - Bv) J - (Bv - Bv') J2 for J = 0, 1, 2, ...

>0 >0

For ΔJ = - 1 or J - 1 ← J, we speak of absorption peaks within the so-called P-branch. Their

wavenumbers ν are

ν = ν0 - (Bv + Bv') J - (Bv - Bv') J2 for J = 1, 2, 3, ...

The distance Δν between absorption line J and absorption line J+1 becomes

R- Δ&nu = 2(2Bv' - Bv) - 2(Bv - distance

branch: Bv') J decreases
distance
P-branch: Δν = 2Bv + 2(Bv - Bv')J
increases

For Bv≈ Bv' , this distance is approximately 2B. The distance between the first transitions of the
two branches is Δν ≈ 4Bv

Almost all diatomic molecules display such spectra with two branches R and P. As an example,
hydrogen chloride is shown. Here, a natural mixture of isotopes served as a sample. Therefore,
two species of HCl molecules with a relative difference of 0.15 percent in their reduced mass are
present and some splitting occurs. The shift respective the wavenumbers of the lines of H35Cl
and H37Cl is Δω ≈ 2cm-1.
vibrational levels rovibrational levels
Ev = (v + ½) hω0 Er = B ⋅ J (J + 1)

P-branch R-branch
ΔJ = −1 ΔJ = +1
Vibrational and rotational energy levels respective transitions
 of a diatomic molecule

Some molecules display additional lines in the gap between the P- and the R-branch. These lines
are connected to transitions with ΔJ = 0 and form the so-called Q-branch. As the rotation of the
system is maintained, the axis of rotation must shift (ΔK ≠ 0) and a change of the angular
momentum of electron orbitals must occur. If we consider diatomics, lines of a Q-branch must
also have such an angular momentum which contributes to the total angular momentum of the
molecule.

The quantum number Λ (recall chapter "Term symbols and

selection rules") denotes the projection of this orbital's
angular momentum onto the molecule's axis. For Λ = 0,
nothing changes. For the molecular total momentum, which
includes rotation of nuclei and electrons, the relation |J| ≥
Projection of the electron's
|Λ| applies.
rotation onto the axis of the
The respective energy levels are analogous to those of the
molecule:
symmetric top. Here, the constant A is in connection with
Λ = 0, 1, 2, ...
the momentum of electron orbitals. Note that A >> B.

EJ = BJ (J + 1) + (A - B) Λ2
due to rotation of nuclei due to electrons

For Λ ≠ 0, there are new selection rules: Besides ΔJ = ±1, as well transitions with ΔJ = 0 are
allowed.

With the NO molecule, we have this situation, but due to spin-related phenomenona, a detailed
analysis is quite complicated. With no regard to the spin, there is the following approach to the
lines of the Q-branch:

E(v',J) - E(v,J) = ν0 + Bv' J(J+1) + (A-Bv')Λ2 - BvJ(J+1) - (A-Bv)Λ2

ν = ν0 - (Bv-Bv')J(J+1) + (Bv-Bv')Λ2

As Bv ≈ Bv' , the lines within this branch lie very close to each other.

For the symmetric top, we have the following selection rules

ΔJ = ±1 for K
diatomic molecules
ΔK = 0 =0
parallel band ΔJ = 0, ±1 for K diatomic molecules, electronic
≠0 contribution to J
ΔK = ±1
perpendicular ΔJ = 0, ±1
band
Of course, the intensity of rovibronic lines depends on the probability of a transition and on the
occupancy of the involved states. In cases where ν = 0 is the only occupied vibrational level, the
intensity of lines is proportional to the population NJ and the so-called Hönl-London-Factor SJ
for this rotational state J.

I ∝ NJ · |µJ'J|2
I ∝ NJ · SJ

As the transition probabilities for a simple rotator at high rotational states are in a quite narrow
range, mainly the vibrational ground state distribution over J rules the intensity of lines. To find
out the most probable rotational state, we fall back on Boltzmann's theory:

An estimation of the distribution is feasible if the distance betweeen the rotational levels is much
smaller than the product kT, a condition which is fulfilled for temperatures around 300 Kelvin.
We use dNJ/dJ = 0 as condition for a maximum.

For Hydrogen chloride, we recieve a value around 2 or 3, for Hydrogen Iodide around 50. This
approach paves the way to calculate temperatures, e.g. the temperature of the stratosphere, by
using line intensities.

Chemical reactions often form products in abnormal state distributions. Provided the transistion
probabilities, measurements of line intensities allow conclusions about such distributions. E.g.,
among the reactions that yield Hydrogene Fluoride, there are many where the HF molecules
initially appear in some vibrationally excited state. Related techniques have been used by John
C. Polanyi. In 1986, he, D.R. Herschbach and Y.T. Lee have been awarded with the nobel prize
for their contributions to a more detailed understanding on reaction dynamics on the molecular
level.