Vibrational (IR) Spectroscopy

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IR Spectroscopy

I. Introduction
C. The IR Spectroscopic Process
1. The quantum mechanical energy levels observed in IR spectroscopy are those of
molecular vibration

2. We perceive this vibration as heat

3. When we say a covalent bond between two atoms is of a certain length, we are
citing an average because the bond behaves as if it were a vibrating spring
connecting the two atoms

4. For a simple diatomic molecule, this model is easy to visualize:

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IR Spectroscopy

I. Introduction
C. The IR Spectroscopic Process
5. There are two types of bond vibration:
• Stretch – Vibration or oscillation along the line of the bond

H H
C C
H H

symmetric asymmetric

• Bend – Vibration or oscillation not along the line of the bond

H H H H
C C C C
H H H
H
scissor rock twist wag
in plane out of plane
Infrared Spectroscopy

C. The IR Spectroscopic Process

6.As a covalent bond oscillates – due to the oscillation of the dipole
of the molecule – a varying electromagnetic field is produced

7.The greater the dipole moment change through the vibration, the
more intense the EM field that is generated

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Infrared Spectroscopy

C. The IR Spectroscopic Process

8. When a wave of infrared light encounters this oscillating EM field
generated by the oscillating dipole of the same frequency, the two
waves couple, and IR light is absorbed

9. The coupled wave now vibrates with twice the amplitude

IR beam from spectrometer

“coupled” wave

EM oscillating wave
from bond vibration

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Infrared Spectroscopy

D. The IR Spectrum
1. Each stretching and bending vibration occurs with a characteristic frequency as
the atoms and charges involved are different for different bonds

The y-axis on an IR
spectrum is in units of %
transmittance In regions where
no osc. bond is
interacting with IR
In regions where the EM light, transmittance
field of an osc. bond nears 100%
interacts with IR light of
the same n –
transmittance is low (light
is absorbed)

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Morse PE

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 v
Convergence
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 Anharmonicity

Fundamental: v = 1  0 Overtone:
Hot band: v = 2  1; v = 3  2, etc. v = 2  0; v = 3  0, etc.

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Vibrations of Polyatomic Molecules

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 Vibrational Spectroscopy
For polyatomic molecules, the situation is more complicated because there are more possible
types of motion. Each set of possible atomic motions is known as a mode. There are a total
of 3N possible motions for a molecule containing N atoms because each atom can move in
one of the three orthogonal directions (i.e. in the x, y, or z direction).

A mode in which all the atoms are moving in the same

direction is called a translational mode because it is equivalent
to moving the molecule - there are three translational modes
for any molecule.

A mode in which the atoms move to rotate (change the

orientation) the molecule called a rotational mode - there are
three rotational modes for any non-linear molecule and only
two for linear molecules.

Translational Rotational
modes modes
The other 3N-6 modes (or 3N-5 modes for a linear molecule) for a molecule correspond to
vibrations that we might be able to observe experimentally. We must use symmetry to figure
out what how many signals we expect to see and what atomic motions contribute to the
particular vibrational modes. 18
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Linear Molecules

• 3 DOF to define translation

• 2 DOF to define rotation

• 3N – 5 ≡ number of vibrational modes

Nonlinear Molecules

• 3 DOF to define translation

• 3 DOF to define rotation

• 3N – 6 ≡ number of vibrational modes

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Fermi Resonance Accidential degenercies

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 Normal modes of vibration:
Description of the vibrations of CO2

using ν and ν .
L R

Stretching modes
are not independent

Definition: Independent synchronous motion of atoms or groups of atoms that may be

excited without leading to the excitation of any other normal mode and without involving
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translation or rotation of a molecule as a whole.
Alternative description of the vibrations of
CO2 using linear combination of νL and νR.

Symmetric and asymmetric stretching modes are independent

and therefore are normal modes 26
Fig 13.40(c) Alternative description of the vibrations of
CO2 using linear combination of νL and νR.

The two scissoring modes are also normal

modes

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Fig 13.41 The three normal modes of H2O

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