Infrared Spectroscopy

Provides information about the vibrations of

functional groups in a molecule

Therefore, the functional groups present in a

molecule can be deduced from an IR spectrum
IR Spectroscopy

I. Introduction
8. The entire electromagnetic spectrum is used by chemists:
Frequency, n in Hz
~1019 ~1017 ~1015 ~1013 ~1010 ~105

Wavelength, l
~.0001 nm ~0.01 nm 10 nm 1000 nm 0.01 cm 100 m

Energy (kcal/mol)
> 300 300-30 300-30 ~10-4 ~10-6

g-rays X-rays UV IR Microwave Radio

nuclear core electronic molecular molecular Nuclear Magnetic
excitation electron excitation vibration rotation Resonance NMR
(PET) excitation (p to p*) (MRI)
(X-ray
cryst.)

Visible
IR Spectroscopy

I. Introduction

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:

Molecules are made up of atoms linked by chemical bonds.
The movement of atoms and chemical bonds like spring and
balls (vibration)
IR: Masses, Atoms and Springs
A Model: Picture the atoms of a diatomic molecule
as point masses connected by springs (bonds).

As a first approximation use Hooke’s Law

F = -kx
F = force, restoring back to equilibrium
position

k = characteristic stretching constant

x = displacement from the equilibrium

position
IR Stretching Frequencies of two
bonded atoms:
What Does the Frequency, ,
Depend On?
1 k m1 m2
 mr 
m1  m2
2 mr

n = frequency
k = spring strength (bond stiffness)
mr = reduced mass (~ mass of largest atom)
Molecular Vibrations and IR Spectroscopy
 Vibrations
What is a vibration in a molecule?
Any change in shape of the molecule- stretching of
bonds, bending of bonds, or internal rotation
around single bonds

There are two main vibrational modes :

1. Stretching - change in bond length (higher
frequency)

Stretching vibration
Stretching Types

Symmetric Asymmetric

2. Bending - change in bond angle (lower frequency)

Bending Types

In-plane (Scissoring) Out-plane (Twisting)

Modes of vibrations
Stretching: change in bond distance.
Occurs at higher energy: 4000-1250 cm1.

Bending: change in bond angle.

Occurs at lower energy: 1400-666 cm1.

H 2O

-CH2-
Vibrational frequencies in IR are expressed in wave number
rather than wave length

Expressed in cm-1

Wave number is directly proportional to the energy

IR spectrum extends up to 400 cm-1 to 4000 cm-1

Wave length range is 2.5 to 25 µm

 Matter/Energy Interactions

• What happens when a sample absorbs UV/Vis energy?

p*
excitation of ground state electrons
UV/Vis p  p*
(typically p and n electrons) sample transition
Eelectronic increases momentarily (200 nm)

• What happens when a sample absorbs IR energy?

stretching and bending of bonds
IR
(typically covalent bonds) -O-H -O —H
Evibration increases momentarily (3500 cm )-1
 The IR Region
 Just below red in the visible region
 Wavelengths usually 2.5-25 mm
 More common units are wavenumbers, or cm-1, the
reciprocal of the wavelength in centimeters
(104/mm = 4000-400 cm-1)
 Wavenumbers are proportional to frequency and
energy

• The IR region is divided into three regions: the near, mid,

and far IR. The mid IR region is of greatest practical use
to the organic chemist.
 Can a vibration change the dipole moment of a
molecule?

 Asymmetrical stretching/bending and internal

rotation change the dipole moment of a molecule.
Asymmetrical stretching/bending are IR active.

 Symmetrical stretching/bending are IR less

active or may be not

 Infrared active vibrations (those that absorb

IR radiation) must result in a change of dipole
moment
Fundamental Vibrations (Absorption Frequencies)
A molecule has as many as degrees of freedom as
the total degree of freedom of its individual
atoms.
• Each atom has 3 degree of freedom (x,y,z)
• A molecule of n atoms therefore has 3n degrees of
freedom.
• Non linear molecules (e.g. H2O)
Vibrational degrees of freedom or Fundamental Vibrations
= 3n – 6

H H H H H H
O O O

Symmetrical Asymmetrical Scissoring

Stretching (υs OH) Stretching (υas OH) (δs HOH)
3652 cm-1 3756 cm-1 1596 cm-1
• For linear molecule (e.g. CO2) :
Vibrational degrees of freedom or Fundamental Vibrations
= 3n – 5

O C O O C O

Symmetrical Asymmetrical
Stretching (υs CO2) Stretching (υas CO2)
1340 cm-1 2350 cm-1

O C O O C O

Scissoring (bending out

of the plane of the paper) Scissoring (bending in
(δs CO2) 666 cm-1 the plane of the paper)
(δs CO2) 666 cm-1