Subject Chemistry

Paper No and Title 8/ Physical Spectroscopy

Module No and Title 22/ Breakdown of the Born-Oppenheimer approximation.

Selection rules for rotational-vibrational transitions. P, R
branches.
Module Tag CHE_P8_M22

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE No. : 22 (BREAKDOWN OF THE BORN-
OPPENHEIMER APPROXIMATION. SELECTION RULES
FOR ROTATIONAL-VIBRATIONAL TRANSITIONS. P, R
BRANCHES)
 TABLE OF CONTENTS
1. Learning Outcomes
2. Introduction

3. Breakdown of the Born-Oppenheimer approximation.

4. The Interaction of Rotations and Vibrations

5. Summary

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE No. : 22 (BREAKDOWN OF THE BORN-
OPPENHEIMER APPROXIMATION. SELECTION RULES
FOR ROTATIONAL-VIBRATIONAL TRANSITIONS. P, R
BRANCHES)
 1. Learning Outcomes

After going through this module, you should be able to:

(a) Use the Born-Oppenheimer approximation to understand the effect of rotational
transitions on vibrational spectra
(b) Understand the breakdown of this approximation and interpret the observed
spectra.
(c) Use data from real vibrational spectra to obtain fundamental vibrations and
rotational constants.

2. Introduction
The vibrational spectra of diatomic molecules is expected to show a few lines corresponding to a
fundamental and a few overtones, as well as a hot band corresponding to transitions from the
excited level. However, the gas phase spectra are more complicated than this, and the distinctive
shape of the contours gives us more information about the molecule.

3. Breakdown of the Born-Oppenheimer Approximation

When considering pure vibrational or pure rotational transitions, we assume that the two are
independent. This is essentially the Born-Oppenheimer approximation, which states that since the
energies involved are very different, they do not interact. Consider a molecule that is
simultaneously undergoing vibration and rotation. The rotational energy level separations are of
the order 1 - 10 cm-1 while the vibrational energy level separations are of the order of 3000 cm-1.
Thus, to a good approximation, a molecule executes rotational and vibrational motions
independently. According to the Born-Oppenheimer approximation, the total energy of such a
molecule can be written as the sum of the rotational and vibrational energies:

ETotal = E rot + E vib (1)

In wavenumber terms, the total energy would be as

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE No. : 22 (BREAKDOWN OF THE BORN-
OPPENHEIMER APPROXIMATION. SELECTION RULES
FOR ROTATIONAL-VIBRATIONAL TRANSITIONS. P, R
BRANCHES)
 ~ ~ ~
S (υ , J ) = BJ ( J + 1) − DJ 2 ( J + 1) 2 + HJ 3 ( J + 1) 3 + ...
2
⎛ 1 ⎞ ⎛ 1 ⎞
+ ⎜υ + ⎟ω e − ⎜υ + ⎟ ω e χ e
⎝ 2 ⎠ ⎝ 2 ⎠

The rotational constants are much smaller than the vibrational frequencies and the centrifugal
distortion constants are still smaller and can be ignored in comparison with the vibrational
energies. Thus we have:

2
~ ⎛ 1 ⎞ ⎛ 1 ⎞
S (υ , J ) = BJ ( J + 1)+ ⎜υ + ⎟ω e − ⎜υ + ⎟ ω e χ e (2)
⎝ 2 ⎠ ⎝ 2 ⎠

The selection rules are the same as those for the individual transitions, i.e.

Δυ = ±1 , ± 2 , ...
(3)
ΔJ = ±1

An analytical expression for the spectrum may be obtained by applying the selection rules to
equation (2). Considering only the υ = 0, J = J” → υ = 1, J = J’ transition, we can have

ΔS~( J ,υ ) = S ( J ' ,1) − S ( J " ,0) ~

= BJ ʹ′( J ʹ′ + 1) + (3 / 2)ω e − (9 / 4)ω e χ e − ( BJ ʹ′ʹ′( J ʹ′ʹ′ + 1) + (1 / 2)ωe − (1 / 4)ω e χ e )

~
= ω e (1 − 2χ e ) + B ( J ʹ′ − J ʹ′ʹ′)( J ʹ′ + J ʹ′ʹ′ + 1)

~
= ω0 + B ( J ʹ′ − J ʹ′ʹ′)( J ʹ′ + J ʹ′ʹ′ + 1)

where ω 0 = ω e (1 − 2χ e ) .

In the case where ΔJ = +1, i.e. J′ = J′′+1, we obtain

~
ΔS ( J " ,υ ) = ω0 + 2B ( J ʹ′ʹ′ + 1), J ʹ′ʹ′ = 0 ,1, 2 , ...

In the case where ΔJ = -1, i.e. J′′ = J′+1, we get

~
ΔS ( J ' ,υ ) = ω0 − 2B ( J ʹ′ + 1) , J ' = 0 , 1 , 2 , ...
CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)
MODULE No. : 22 (BREAKDOWN OF THE BORN-
OPPENHEIMER APPROXIMATION. SELECTION RULES
FOR ROTATIONAL-VIBRATIONAL TRANSITIONS. P, R
BRANCHES)
 These may be combined to yield

~
ΔS ( J ,υ ) = ω0 + 2Bm, m = ±1 , ± 2 , ... (4)

where ω 0 is known as the band origin or band centre. Equation (4) represents the combined
~
vibration-rotation spectrum. It will consist of evenly spaced lines (spacing = 2 B ) on each side of
the band origin ω 0 but since m ≠ 0, the line at ω 0 will not appear.

Lines to the low side of ω 0 (when m is negative, i.e. ∆J = -1) are referred to as the P branch, while
those to the high frequency side (m positive, ∆J = +1 ) are referred to as the R branch (Fig. 1).

Figure 1: Schematic diagram showing the P and R branches of a diatomic molecule. Lines on the
left side are the P branches and those on the right side are R branches. The band centre is missing.
CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)
MODULE No. : 22 (BREAKDOWN OF THE BORN-
OPPENHEIMER APPROXIMATION. SELECTION RULES
FOR ROTATIONAL-VIBRATIONAL TRANSITIONS. P, R
BRANCHES)
 From Figure 1, it is clear that the band centre is the average of P(1) and R(0). Table 1 gives part of
the IR spectrum of CO. From the table we see that the band centre is at 2143.255 cm-1, while the
average line separation near the centre is 3.83 cm-1. This immediately gives:

~ ~
2 B = 3.83 cm-1 and B = 1.915 cm-1.

Table 1: Part of the IR spectrum of CO

Line cm-1 separation, cm-1 Line cm-1 separation, cm-1

P(1) 2139.43 3.88 R(0) 2147.08 3.78
P(2) 2135.55 3.92 R(1) 2150.86 3.73
P(3) 2131.63 R(2) 2154.59

~
This is in satisfactory agreement with the more precise value of B = 1.92118 cm-1 derived from
~
microwave spectroscopy. From B , the moment of inertia, I, and the bond length can be
determined.

---

Example 1: The four central lines in the high resolution υ =1 ← υ = 0 infrared spectrum
of H37Cl occur at 2837.6, 2858.8, 2899.2 and 2918.6 cm-1.
Deduce as much as possible about the molecule.
Would the corresponding lines in H35Cl lie at the same spectral positions?

Solution

The band centre is at the average of the two central lines, i.e. 2879.0 cm-1. This is equal
~
to the fundamental frequency, ω0. The 4 B separation at the centre is 40.4 cm-1, giving a
~
value of 10.1 cm-1 for B . The moment of inertia is

h − 47 2
I= ~ = 2.771 × 10 kg m
2
8π Bc

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE No. : 22 (BREAKDOWN OF THE BORN-
OPPENHEIMER APPROXIMATION. SELECTION RULES
FOR ROTATIONAL-VIBRATIONAL TRANSITIONS. P, R
BRANCHES)
 The reduced mass is given by

m H mCl 1.0078 × 36.9659 × 10 −3

µ= = = 1.629×10-27 kg
(m H + mCl ) N A 37.9737 × 6.022 × 10 23

I 2.771 × 10 −47
Therefore, r = = − 27
= 1.304×10-10 m = 0.1304 nm
µ 1.629 × 10

Since the positions of the lines depend on the reduced mass, the lines for H35Cl will be
at a different position. The reduced mass of H35Cl is smaller and hence its moment of
inertia is smaller and rotational constant larger, so the lines will have larger separation.

The fundamental vibration frequency will also be higher since it is inversely proportional
to the square root of the reduced mass.

---

4. The Interaction of Rotations and Vibrations

According to the previous discussion, the rotational spacing should be the same. However, this is
not the case. A crowding of lines is seen in the R branch with increasing J, whereas the spacing
increases in the P branch. Apparently, the assumption of independence of vibration and rotation is
in error and there is an interaction between the two.

Since the frequency of vibration is higher than that of rotation, a molecule vibrates 103 times
during the course of a single rotation and so the bond length (and hence the moment of inertia I
~ ~
and B ) also changes continually during the rotation. The rotational constant B depends on the
1
average value of 2 . Further, an increase in vibrational energy is accompanied by an increase in
r
~
vibrational amplitude because of the widening of the potential well, and hence the value of B
will depend on the vibrational quantum number.

This increase is even more pronounced for anharmonic vibrations. An increase in vibrational
energy will lead to an increase in the average bond length. The vibrational constant then varies
even more with vibrational energy. In general, since rav increases with the vibrational energy,

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE No. : 22 (BREAKDOWN OF THE BORN-
OPPENHEIMER APPROXIMATION. SELECTION RULES
FOR ROTATIONAL-VIBRATIONAL TRANSITIONS. P, R
BRANCHES)
 ~
B is smaller in the upper vibrations than in the lower ones. We may express this dependence in
terms of an empirical equation

⎛ 1 ⎞
Bυ = Be − α ⎜υ + ⎟ (5)
⎝ 2 ⎠

where Bυ is the rotational constant in the vibrational level υ, Be is the equilibrium rotational
constant at the potential minimum, and α is a small positive constant.

~ ~
Consider the fundamental vibrational change υ = 0 → υ = 1. The respective B values are B 0 and
~
B1 . For this transition, we will have

ν~ = G( J ' ,υ = 1) − G( J " ,υ = 0)
~ ~ (6)
= ω0 + B1 J ʹ′( J ʹ′ + 1) − B0 J ʹ′ʹ′( J ʹ′ʹ′ + 1)

where

ω 0 = ω e (1 − 2 χ e )

We then have the two cases:

Case 1

ΔJ = +1 , J ʹ′ = J ʹ′ʹ′ + 1
~ ~ ~ ~ (7)
ν~ = ω 0 + ( B1 + B0 )( J ʹ′ʹ′ + 1) + ( B1 − B0 )( J ʹ′ʹ′ + 1) 2

where J″ = 0, 1, 2, …

Case 2

ΔJ = −1 , J ʹ′ʹ′ = J ʹ′ + 1
~ ~ ~ ~ (8)
ν~ = ω 0 − ( B1 + B0 )( J ʹ′ + 1) + ( B1 − BO )( J ʹ′ + 1) 2

where Jꞌ = 0, 1, 2, …

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE No. : 22 (BREAKDOWN OF THE BORN-
OPPENHEIMER APPROXIMATION. SELECTION RULES
FOR ROTATIONAL-VIBRATIONAL TRANSITIONS. P, R
BRANCHES)
 These two equations may be combined to yield:

~ ~ ~ ~
ν~P , R = ω 0 + ( B1 + B0 )m + ( B1 − B0 )m 2 (9)

with m = ±1, ±2, ±3, …

The positive m values refer to R branches and the negative ones to P branches.

Equation (9) allows us to fit the observed transitions to a quadratic equation, from which the
various terms can be determined.

~ ~
Since B1 < B0 because the internuclear separation is higher in higher vibrational states, the
spacing in the R branches decreases with increasing J and the opposite is observed for the P
branches. This gives a distinctive shape to the spectrum.

5. Summary
• An approximation that can be used to understand vibration-rotation spectra is the Born-
Oppenheimer approximation, which states that since the energy scales are different, the
two motions can be treated independently.
• The two selection rules also remain the same. Application of the selection rules predicts
two branches in the spectra, but the band centre itself is missing.
• However, analysis of the spectra yields information about the vibrational frequencies and
rotational constants and all corresponding molecular parameters can be determined.
• However, analysis of real spectra shows a crowding of lines at the higher wavenumber R
branches, and a spacing out of the P branches with increasing J.
• This implies that the rotational constant is not independent of the vibrational quantum
number and decreases with increasing υ since the average bond length increases with
increasing amplitude of vibration.

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE No. : 22 (BREAKDOWN OF THE BORN-
OPPENHEIMER APPROXIMATION. SELECTION RULES
FOR ROTATIONAL-VIBRATIONAL TRANSITIONS. P, R
BRANCHES)