Spectroscopy - Rotational Spectroscopy - Wikiversity

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A molecule can store

Subject classification: this is a chemistry resource.
energy in its tumbling

motion.
This is only relevant in
Type classification: this is a lesson resource.
the gas phase where

molecules are in
continual motion and are free to rotate
unhindered.
Rotational motion at the molecular level
is quantized in accordance with quantum
mechanical theory.
Transitions between discrete rotational
energy levels give rise to the rotational
spectrum of the molecule (microwave
spectroscopy).
We will study:
classical rotational motion, angular

momentum, rotational inertia
quantum mechanical energy levels
selection rules and microwave
(rotational) spectroscopy
the extension to polyatomic molecules
Classical rotational motion

Rotational energy is kinetic energy
associated with a tumbling motion.
Consider a particle with mass m, rotating
with angular velocity ω, at a distance R
from a given axis.
This particle has angular momentum J

|J| = I ω where |J| is the magnitude of the
angular momentum vector, and I is the
moment of inertia (the rotational
equivalent of mass).
Where do we use rotational spectroscopy?

The 2.45 GHz frequency used by
microwave ovens is the most ideal one for
causing water molecules to rotate at their
fastest possible rate. There is also the
added bonus that this frequency is not
used for communication, so microwave
ovens do not interfere with cell phones,
wireless internet, televisions and so on.
Diatomic molecules: the rigid

rotor
Remember that a molecule does not distort
under rotation.
R = r1 + r2 (Eq. 1)
The axis passes through the centre of

mass (C):
(Eq. 2)
Moment of inertia:
(Eq. 3)
Using equations 1, 2 and 3:

μ is the reduced mass.
Example: For 1H35Cl -
(Remember that u = atomic mass unit =

1.661x10-27 kg)
Rotational energy levels
Classical:
Quantum mechanical: solve the

Schrödinger equation for the rigid diatomic
rotor.
EJ is measured in Joules
J is the rotational quantum number (= 0,
1, 2, ...)
Converted to Rotational
wavenumbers: constant:
The units of εJ and B = cm-1
Below are the rotational energy levels for

diazenylium, N2H+.
N2H+
J = 0 → εJ = 0 0
J = 1 → εJ = 2B cm-1 ≈3 cm-1
J = 2 → εJ = 6B cm-1 ≈10 cm-1
Important points to notice:
The energy of the ground state (J = 0) is

zero - because the molecule is not
rotating.
As J increases, the molecules rotate
more and more quickly - as a result, the
energy levels are more widely spaced
apart.
The energy level separations are
compatible with the microwave region of
the EM spectrum.
But what about spectroscopic transitions

between energy levels? And what about the
selection rules for microwave
spectroscopy?
Gross selection rule …
Gross Selection Rule: The requirement for

a permanent dipole.
For example, take a rotating HCl molecule.
The fluctuation in its dipole component has
an identical form to the fluctuation in the
electric field of EM radiation (see the
electromagnetic wave in Lesson 1).
As a result, the electric field of the EM wave

exerts a torque on the dipole of the HCl
molecule.
This means that energy can be absorbed or

emitted, giving rise to a rotational
spectrum.
Gross Selection Rule: molecules with
permanent dipoles are microwave active
(the molecule must be polar), e.g.
heteronuclear diatomics - HCl, CO, NO,
etc.
Homonuclear diatomics are microwave

inactive (e.g. O2, N2, etc.)
In other words, a dipole must be present

in the molecule for you to get a rotational
spectrum.
Transitions between energy levels …
Specific Selection Rule: During a

transition, the rotational quantum number
must change by 1 unit only, i.e. ΔJ = ±1
(angular momentum is conserved)
In other words, only transitions between

neighboring energy levels are possible.
Below is an example rotational spectrum.
The top part shows the rotational energy
levels, εJ. The bottom part shows the
microwave spectrum as observed from an
experiment.
Each absorption (red arrow) complies with

ΔJ = +1.
As a result of the equations in the box
above, you get a series of spectral lines,
each separated by 2B.
For CO, Δε = 3.86 cm-1. For HCl, Δε = 21.18

cm-1.
You'd get the same values for emission

spectroscopy, except ΔJ = -1.
After obtaining a microwave spectrum

from experiment, you measure nexp in cm-1.
(The distance between spectral lines is
Δnexp). From this you can work the
rotational constant B, because Δvexp (this is
the intensity of each spectral line) = 2B.
Using the formulae in the green boxes
further up this page you can work out B
and I. Now you can calculate molecular
properties (such as R, μ) to a high degree of
accuracy.
Rotational energy level
population
Note that the most intense band is not the
first line in the spectrum. Why?
Remember the 3 factors from Lesson 1:
1. Amount of sample
2. Population of energy states
3. Selection rules
We need to consider number 2 - the

Boltzmann distribution AND degeneracy.
Nf and Ni are the population of molecules in
energy levels ef and ei with degeneracy
gfand gI.
From quantum mechanics, the degeneracy

of each eJ level = 2J + 1
J = 0 1 (non-degenerate)
J = 13 (3-fold degenerate)
Population of excited state relative to

ground state:
Initial J=
ei = e0 = 0 gi = g0 = 1
state: 0
ef = eJ = BJ(J + gf =
Final state: J
1) (2J+1)
Δε = εJ - ε0 = BJ(J + 1) →
Example for J = 1 (at T = 300 K):
B = 2 cm-1 Nf/Ni = 2.94

B = 10 cm-1 Nf/Ni = 2.70
The population of the J = 1 level decreases

as the energy level separation (i.e. 2B)
increases.
Degeneracy (the pre-exponential term)
moves the maximum population away
from J = 0. You can use calculus to
determine the most populated level - the
maximum which occurs when .

For example, at 300K, B = 5 cm-1 → kBT =
208.5 cm-1 → Jmax = 4 (which corresponds
to the 4→5 transition).
Non-rigid rotor
Gray text is additional information provided
for further reading only. This content will
not be tested.
We have assumed so far that the bond

length remains fixed during rotation of the
molecule - this is the rigid rotor model.
However, as the molecule rotates the
atoms are subject to centrifugal forces
which stretch the bonds - this is the non-
rigid rotor model.
Hooke's law states for an elastic bond:
F = restoring force (N)

r = bond length; req = equilibrium bond
length (m)
k = force constant (Nm-1)
c = vibrational frequency (cm-1)
m = reduced mass (kg)
Non-rigid rotor model for diatomic

molecules:
Centrifugal
Non-rigid rotor model
distortion
for diatomic molecules
coefficient
The first term is the rigid rotor model, and
the second term is a correction for the
centrifugal distortion. It is important to
consider this for high values of J.
Centrifugal distortion leads to lowering of

the given energy level (at high J).
Consequently, spectral lines cluster
together at high J and are no longer equally
spaced.
Polyatomic molecules
The majority of molecules are not diatomic
- they can possess rotation around more
than one axis.
The classical expression for energy of a

body rotating about axis a is
With similar expressions for the other axes,

it follows that:
Polyatomic molecules are categorised
according to their moments of inertia
about 3 perpendicular axes:
Linear - one moment of inertia equals

zero: Ia = Ib, Ic = 0. Molecules include CO2,
OCS, C2H2.
Spherical rotor - three equal moments of
inertia: Ia = Ib = Ic. Molecules include CH4,
SiH4, SF6.
Symmetric rotor - two equal moments of
inertia: Ia = Ib ≠ Ic. Molecules include NH3,
CH3Cl, CH3CN.
Asymmetric rotor - three different
moments of inertia: Ia ≠ Ib ≠ Ic. Molecules
include H2O, CH3OH, H2CO.
Calculation of B: Example
Calculate the value of the rotational

constant B for a molecule of carbon
monoxide. The bond length (R) of CO is
0.113 nm.
Solutions
Step 1: Calculate the reduced mass using equation .
Step 2: Calculate the moment of inertia using equation .
Step 3: Calculate the rotational constant using equation .
Notice that a low m and a low R give a high B.

Lesson 3. Vibrational
Spectroscopy
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…

A molecule can store

energy in its tumbling

the gas phase where

classical rotational motion, angular

Classical rotational motion

This particle has angular momentum J

Where do we use rotational spectroscopy?

Diatomic molecules: the rigid

The axis passes through the centre of

Using equations 1, 2 and 3:

Example: For 1H35Cl -

(Remember that u = atomic mass unit =

Quantum mechanical: solve the

The units of εJ and B = cm-1

Below are the rotational energy levels for

The energy of the ground state (J = 0) is

But what about spectroscopic transitions

Gross selection rule …

Gross Selection Rule: The requirement for

As a result, the electric ﬁeld of the EM wave

This means that energy can be absorbed or

Homonuclear diatomics are microwave

In other words, a dipole must be present

Speciﬁc Selection Rule: During a

In other words, only transitions between

Each absorption (red arrow) complies with

For CO, Δε = 3.86 cm-1. For HCl, Δε = 21.18

You'd get the same values for emission

After obtaining a microwave spectrum

Remember the 3 factors from Lesson 1:

We need to consider number 2 - the

From quantum mechanics, the degeneracy

Population of excited state relative to

Example for J = 1 (at T = 300 K):

B = 2 cm-1 Nf/Ni = 2.94

The population of the J = 1 level decreases

maximum which occurs when .

We have assumed so far that the bond

Hooke's law states for an elastic bond:

F = restoring force (N)

Non-rigid rotor model for diatomic

Centrifugal distortion leads to lowering of

The classical expression for energy of a

With similar expressions for the other axes,

Linear - one moment of inertia equals

Calculate the value of the rotational

Step 1: Calculate the reduced mass using equation .

Step 2: Calculate the moment of inertia using equation .

Step 3: Calculate the rotational constant using equation .

Notice that a low m and a low R give a high B.

Last edited 2 years ago by MaintenanceBot

Content is available under CC BY-SA 3.0 unless

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