IR SPECTROSCOPY
IR spectroscopy or vibrational spectroscopy involves the transitions between the
vibrational energy levels of a molecule, having change in dipole moment with
vibration of a bond.
Molecules have quantized vibrational energy levels. The energy gap between
vibrational levels falls in IR region. Therefore absorption of IR photons results in
vibrational excitations.
Absorption of IR radiations falling in the range (wave number 500 - 4000 cm-1) by
molecule results in transitions between vibrational energy levels.
An IR spectrum is a plot of wave number (X axis) vs percentage
transmittance (Y axis)
IR spectrum is called Vibrational – rotational spectrum since Energy required
is less for rotational transitions
• Heteronuclear diatomic molecule like HCl – when they undergo stretching
vibration dipole moment changes with change in inter nuclear distance- IR
active
• Homonuclear diatomic molecule like H2, O2, N2 – No change in dipole moment
with stretching vibration- IR inactive
Mechanism of interaction of IR light with
oscillating dipole moment
During vibration, if there occurs a change in dipole moment, it will lead to the
generation of an oscillating electric field and act as a source of electromagnetic
radiation. Consider the asymmetric stretching vibration of carbon dioxide.
Oscillating dipole generates electric field. When a photon of frequency comes
in resonance with the frequency of vibration of molecule, absorption of a
photon takes place and molecule will be vibrating in next higher vibrational
level.
Calculation of Number of Vibrational Modes
Degree of freedom is the number of variables required to describe the motion of a particle completely.
For an atom moving in 3-dimensional space, three coordinates are required so its degree of freedom is
three. Its motion is purely translational. If we have a molecule made of n atoms (or ions), the degree of
freedom becomes 3n, because each atom has 3 degrees of freedom. since these atoms are bonded
together, all motions are not translational; some become rotational, some others vibration.
The translational degrees of freedom for any molecule is three.
• For a linear molecule however, rotation around its own axis is no rotation because it leave the
molecule unchanged. So there are only 2 rotational degrees of freedom for any linear molecule
leaving 3n-5 degrees of freedom for vibration.
The degrees of vibrational modes for linear molecules can be calculated using the formula: 3n−5
n is equal to the number of atoms within the molecule
Ex: Diatomic molecules (HCl) , 3 x 2 – 5 = 1, one vibrational mode, stretching vibration
Ex: Triatomic molecules (CO2, HCN) , 3 x 3 – 5 = 4
Out of the four vibrational modes only three are IR active. The symmetric stretching
does not involves the change of dipole moment and therefore IR in active. The two
bending modes are equivalent. Therefore only two absorption frequencies are observed
in case of carbon dioxide. 2349 cm-1(asymmetric stretching) & 667 cm-1 (bending
vibration).
Calculation of Number of Vibrational Modes
• For non-linear molecules, all rotational motions can be described in terms of rotations around 3
axes, the rotational degree of freedom is 3 and the remaining 3n-6 degrees of freedom constitute
vibrational motion.
The degrees of vibrational modes for non linear molecules can be calculated using the formula: 3n−6
n is equal to the number of atoms within the molecule
Ex: Water , 3 x 3 – 6 = 3
IR spectrum
• Transmittance percentage is plotted against
wave number in cm-1
Regions of IR spectra
Functional group region- it is the high frequency region, between 4000cm-1-
1500cm-1. This is because the characteristic frequencies for important functional
groups such as C=O, OH, NH occur in this region.
Finger print region- it is the middle frequency region, between 1500cm-1-700cm-1.
In this region complex absorptions occur providing a unique fingerprint for every
molecule.
The pattern of bands in this region are dependent on the structure of the molecule
This pattern is very sensitive and changes even on minor changes in the structure.
Thus this part is the fingerprint of a compound.
If the two samples gives similar pattern of bands in fingerprint region, this can be
considered as a proof that the two samples are of the same compound.
Determination of force constant
• The fundamental frequency of vibration or wavenumber is directly
proportional to square root of force constant k (bond strength) and is
inversely proportional to square root of reduced mass of the vibrating
atoms.
Applications
By comparing ir spectra of given sample with ir spectra of pure compound.
