First Week--End Topic:

Rovibrational Spectra
Background
(this section is a development of the content of the green
Slides in the theory material. Skip the background section if you have worked them through)
Rovibrational spectroscopy deals with transitions between rovibrational states, that is, quantum states
with precise vibrational and rotational motion types. As is the rule in spectroscopy, from the
wavelengths of these transitions, important structural information on the molecules can be obtained.
Rotational and vibrational energies are quantized. The characteristics of the rovibrational states can be
computed quite accurately, depending on the model used to describe the rotational and vibrational
motions. The most sophisticated
histicated approach is anharmonic oscillator model for vibration and the nonrigid rotor for rotation. However, in the following discussion a good starting point will be provided by
the simpler rigid-rotor and harmonic oscillator models,
models to which corrections
ns for their deficiencies will
be incorporated.
Uncoupled Harmonic Oscillator+Rigid Rotor Models
In the harmonic oscillator model used as the simplest description to vibration, the potential energy is
actually a parabola centered at the equilibrium interatomic distance,
. This simple model yields
energy levels that are equally spaced, and only a vibrational transition will be observed, corresponding
to the transition from the vibrational ground state
(about the only sufficiently populated) to the first
vibrational excited state. Because the energy
difference is much smaller in rotational energy
levels, the effect of their existence consists in the
splitting of the vibrational band into a multitude of
other bands, separated by a minute energy
difference (when compared to the
t
vibrational
transition). Hence, we will only appreciate the
rotational structure of a vibrational band if we
carry out the measurements with a sufficiently fine
phase CO in the spectral
energy scale. As an example, Figure B.1 below Figure 1: Absorption spectrum of gas-phase
zone where the fundamental vibrational band occurs (v=0 to
gives the spectrum of the fundamental vibrational
vibratio
v=1). The harmonic oscillator model would predict a single
-1
line exactly where the gap is at the center. Note that
band of CO, appearing at about 2140 cm .
frequency (and energy) increases to THE LEFT (source:
Wikipedia)

As in the case of vibrational energy, rotational

energy is quantized. The simplest model for the rotation of a molecule is that of the rigid rotor, which
assumes that the molecule has a rigid internal structure (a fixed interatomic distance). In this model, and
assuming that the rotational and vibrational motions are independent (uncoupled),
(uncoupled) and thus, do not
interfere with each other, the energy of a molecule depends on two quantum numbers:
(which
quantizes rotational motion) and (which does the same for vibrational motion). The expression for the
energy is
,

(1)

In this equation, the first term quantizes vibrational energy: indicates the vibrational quantum number
(0,1,2,...) and
is the equilibrium vibrational frequency. The second term quantizes the rotational
energy; is the rotational quantum number (0,1,2,...), and
(the rotational constant) depends on the
equilibrium internuclear distance
via the inertia moment :
(2)
and

is the reduced mass of the diatomic molecule

(3)

Besides , a second quantum number , + 1, ,0, 1, ) is necessary to completely

determine the rotational state of the diatomic.
does not affect the energy and all rotational states
with different value for but equal value of are degenerate. This means that rotational energy levels
are 2 + 1 times degenerate. This will have effect on the intensity of the spectral lines, though.
The spectrum arises from transitions between rovibrational states (states with precise rotational and
vibrational quantum numbers), and implies possible changes to their quantum numbers. To understand
the spectrum, it is necessary to rely on quantum mechanics to demonstrate that not all transitions are
possible, and that a selection rule controls which transitions are allowed. It is found that allowed
transitions satisfy simultaneously
= 1, = 1

(4)

It is this selection rule that limits the possible transitions and leads to a simple spectrum like the one
depicted in Figure 1. From the expression of the energy above (Equation 1), it is easy to derive the
following expressions for the energy difference for rovibrational transitions where either:
= +1, = +1:

)+,

+2

( + 1) = 0,1,2,3,

(5a)

= +1, = 1:

)+, -)

= 1,2,3,

(5b)

(in the above expressions, is the starting rotational level). Because of the relation of energy to
frequency, = , these two different possibilities lead to two series of spectral lines, one for
= +1 (slightly to higher energy, or frequency, called R branch, equation 5a) and = 1 (slightly to
lower energy, or frequency, called the P branch, equation 5b).
R branch:
P branch:

+2

( + 1)

(6a)
(6b)

The equilibrium vibrational frequency

provides us with the central position of the vibrational band.
The second term provides the rotational fine structure with bands separated evenly by a value 2 to
both sides of the fundamental vibrational frequency . Curiously enough, there is no transition with
exactly this frequency, as the selection rule forbids = 0: it is then important to notice that there is an
empty hole just at in the spectrum (q.v. Figure 1).
Rotation-Vibration Coupled Model
Equations 6a and 6b describe a spectrum with equally spaced lines in the P and R branches (spacing is
2 ). Actually, it is found that this spacing is not constant, and that it varies slightly along each branch;
the discrepancy is due to the fact that the uncoupled rotation+vibration model is limited. To improve it,
one needs to introduce some kind of coupling between the rotational and vibrational motions: this is

admitting that the way a molecule rotates depends on the way it vibrates. The simplest way to
introduce this coupling consists of analyzing the effect on the interatomic distance that the vibrational
excitation has. In fact, it is only true that =
for the harmonic oscillator model of vibration, as the
potential energy curve is completely symmetric with respect to . If vibration is anharmonic, it can be
shown that depends on the vibrational level : the higher the quantity of vibrational energy, the
more stretched the molecule will be on average. This leads to an inertia moment that depends also on
. In the end, the rotational constant depends on the vibrational energy level, so that it is now to be
written as (notice the reference to the quantum number of vibration as a subindex of the rotational
constant):
=

(7)

Notice that now the rotational constant gets smaller upon increasing vibrational energy level. This is the
same as saying that the inertia moment gets larger upon increasing vibrational energy level, or in order
words, that the higher in vibrational levels one goes, the larger the value of the interatomic distance
gets. The new constant 1 depends only on the molecule and is called rotation-vibration coupling
constant.

Further Improvements
The previous model makes use of the harmonic oscillator and the rigid rotor, but includes rovibrational
coupling. It is possible that need for more precision is there: in this case, one might consider the
anharmonic oscillator instead of the harmonic oscillator, or include centrifugal distortion to replace the
rigid rotor. The process is the same as followed so far, just with the necessary changes in the state
energy (Equation 1), to propagate throughout.

Questions

Relative Intensity

Below you will see a simulation of the rovibrational spectrum of HCl. The list of some frequencies is to
-1
be found next to the spectrum (in cm ).

2700

2997,9
3017,2
3035,8
3053,8
3071,0
3087,7
3103,6
3118,9
2800

2900

3000

3100

2957,4
2936,2
2914,3
2891,7
2868,5
2844,6
2820,0
2794,8

3200

Frequency (cm-1)

With this information, and using the rovibrational coupled model (harmonic oscillator + rigid rotor),
answer the following questions:
1.

2.

identify in the above graph the P and R branches, and label them with a subscript
corresponding to the original rotational state for each line (That is, R0 for the rotational
transition 10, P1 for the transition 01, and so on).
Find the value of the harmonic frequency .

3.
4.
5.
6.

Find the value of the rotational constants + and ) .

Find the value of the rovibrational coupling 1 and the rotational constant .
Obtain the value of the interatomic distance derived from each of the three rotational
constants you have obtained.
Discuss the physical interpretation of the results obtained (namely, the three interatomic
distances you have derived).