Vibrational or Infra-red

Spectroscopy

By
Dr.Puspanjali Mishra
Asst.Professor in Chemistry
PMEC, Berhampur
 Molecular Absorptions
• ∆E= 𝑬𝟐 - 𝑬𝟏 = 𝒉𝒗

𝒉𝒗
• Molecule > Electronic Transition → Electronic spectrum or UV-Vis spectrum
𝑼𝑽−𝑽𝑰𝑺

𝒉𝒗
• Molecule > Vibrational Transition → Vibrational spectrum or IR spectrum
𝑰𝑹

𝒉𝒗
• Molecule > Rotational Transition → Rotational spectrum or Microwave
𝑴𝒊𝒄𝒓𝒐𝒘𝒂𝒗𝒆
spectrum
 Infra-Red Spectroscopy
• Infra red radiation is absorbed only when the oscillating dipole moment due to
molecular vibrations interacts with the oscillating electric vector of an infra-red
beam.
• Near Infra-red region: 800 nm – 2500 nm (12,500 cm-1 to 4,000 cm-1)

• Infra-red region: 2500 nm – 15,000 nm (4,000 cm-1 to 667 cm-1)

• Far Infra-red region: 15,000 nm – 200,000 nm (667 cm-1 to 50 cm-1)

• The Infra-red spectroscopy measures the bond vibration frequencies in a
molecule and is used to determine the functional groups.
 Types of molecular Vibrations
• Stretching vibration:
• 1. Symmetric Stretching
• 2. Assymetric Stretching
• Bending Vibration:
• 1. Scissoring
• 2. Rocking
• 3. Wagging
• 4. Twisting
The Bending vibration requires lesser energy and hence occur at
lower frequencies than stretching vibration.
Different modes /types of vibrations
 Types of molecular Vibrations

• https://youtu.be/ZWwLCnuYRys
 Number of molecular vibrations
• Linear molecule:
• No. of vibrations = 3N−5, Where N=no. of atoms
• Example: HCl molecule has 3x2 − 5= 1 vibration
• O=C=O molecule has 3x3 − 5= 4 vibrations.
• H−C≡C−H molecule has 3x4 −5= 7 vibrations.
• Non-linear molecule:
• No. of vibrations = 3N−6, Where N=no. of atoms
• Example: H2O molecule has 3x3−6= 3 vibrations
• Benzene C6H6 molecule has 3x12−6= 30 vibrations
• H3C−C≡C−CH3 molecule has 3x10−6= 24 vibrations.
• H3CCOCH3 molecule has 3x10−6= 24 vibrations.
 IR active molecules
• Out of all vibrations in a molecule, only few vibrations, which are
associated with change in dipole moment, are IR active and absorb IR
radiation at different frequencies.
• IR Active molecules:
• Molecules having permanent dipole moments and exhibiting change in
dipole moments during the vibrations are IR-active molecules. (Ex: CO, HCl)
• Molecules with no permanent dipole moment but some of the vibrational
modes are accompanied by change in dipole moments making these
molecules IR-active. (Ex: O=C=O)
• H2O, HCN, HCl, CO2, NH3 etc: IR active
• IR inactive molecules:
• The molecules which do not have change in dipole moment due to
molecular vibration do not absorb IR radiation and are IR inactive. (Ex:
H2,N2,Cl2)
CCl4, CH4,CH2Cl2 are IR active molecules.

Trans-dichloro ethylene cis-dichloro ethylene

 Infrared spectroscopy
•(IR spectroscopy or vibrational spectroscopy) is the measurement of the
interaction of infrared radiation with matter by absorption, transmission or
reflection.
•Functional group detection.
Theory of molecular vibration:

Vibration energy is quantized

Amplitude increases
Change in dipole moment
 Vibrational frequency
• The vibration of a diatomic molecule may be considered as the vibration of a
simple harmonic oscillator and obeys Hooke’s law.
1 𝑘 1 𝑘
• 𝜔= and 𝜔
ഥ= ,
2𝜋 𝜇 2𝜋𝑐 𝜇

• Where 𝜔 = frequency of vibration in s-1 or Hz,

𝜔
• 𝜔
ഥ= = frequency of vibration in wave number units (cm-1)
𝑐
• 𝑘 = force constant, 𝜇= reduced mass of the molecule.
• According to quantum mechanics, the vibrational energies are quantised.
1
• Ev= (v+ ) hc𝜔,
ഥ ℎ =Plank’s constant, c = velocity of light
2
• where v=0, 1, 2, 3,--- = vibrational quantum number
• Ev=vibrational energy.
 Vibrational energy levels
1
The vibrational energy Ev= (v+ ) hc𝜔,
ഥ
2
where v=0, 1, 2, 3,--- = vibrational quantum number
1 1
When v=0, Ev= (0+ ) hc𝜔
ഥ = hc𝜔
ഥ
2 2
1
zero point vibrational energy= hc𝜔.
ഥ
2 5
hc𝜔
ഥ
2
1 3
v=1, Ev= (1+ ) hc𝜔
ഥ = hc𝜔,
ഥ
2 2 1
hc𝜔
ഥ
2
1 5
v=2, Ev= (2+ ) hc𝜔=
ഥ hc𝜔,
ഥ
2 2
1 7
v=3, Ev= (3+ ) hc𝜔
ഥ = hc𝜔
ഥ,
2 2
1 9
v=4, Ev= (4+ ) hc𝜔
ഥ= hc𝜔
ഥ
2 2
 Selection Rule for vibrational Transition
• Now for a vibrational transition from any level v to v’, The energy difference or energy
absorbed will be given by

• ∆Ev →v’ = Ev’ - Ev = (v’+1/2) hc𝜔

ഥ – (v+1/2) hc𝜔
ഥ = (v’ – v) hc𝜔,
ഥ

• The energy of IR radiation to be absorbed, Ev→v’ = ∆Ev →v’ = (v’ – v) hc𝜔,

ഥ

• The allowed vibrational transitions are

• ∆v = v’ – v = ±1, Ev→v’ = ∆Ev →v’ = (v’ – v) hc𝝎

ഥ = hc𝜔
ഥ = ℎ𝑐 𝜈ҧ ,

𝟏 𝒌
𝝂=𝝎
• ഥ ഥ =
𝟐𝝅𝒄 𝝁

• The frequency (wave number) of absorption(ഥ

𝝂)=The frequency (wave number) of
molecular vibration(𝝎
ഥ )= Fundamental vibration frequency (wave number) .
 Vibrational energy transitions
1
The vibrational energy Ev= (v+ ) hc𝜔,
ഥ
2
where v=0, 1, 2, 3,--- = vibrational quantum number
1 1
When v=0, Ev= (0+ ) hc𝜔
ഥ = hc𝜔
ഥ
2 2
1
zero point vibrational energy= hc𝜔.
ഥ
2 7
hc𝜔
ഥ
2
5
1 3 hc𝜔
ഥ
v=1, Ev= (1+ ) hc𝜔
ഥ = hc𝜔,
ഥ ∆Ev0→1=E1 – E0= hc𝜔
ഥ 2 3
2 2 hc𝜔
ഥ
2

1 5
½ hc𝜔
ഥ
v=2, Ev= (2+ ) hc𝜔=
ഥ hc𝜔,
ഥ ∆Ev1→2=E2 – E1= hc𝜔
ഥ
2 2
1 7
v=3, Ev= (3+ ) hc𝜔
ഥ = hc𝜔
ഥ, ∆Ev2→3=E3 – E2= hc𝜔
ഥ
2 2
1 9
v=4, Ev= (4+ ) hc𝜔
ഥ= hc𝜔,
ഥ ∆Ev3→4=E4 – E3= hc𝜔
ഥ
2 2
Numerical problems:
𝟏 𝒌
ഥ ഥ
Calculation of 𝜈ҧ or 𝜔: 𝝂 =𝝎
ഥ =
𝟐𝝅𝒄 𝝁
,

Calculation of 𝑘: 𝒌 = 𝟒𝝅𝟐𝒄𝟐𝝎
ഥ 2𝝁 = 𝟒𝝅𝟐𝒄𝟐ഥ
𝝂2𝝁
Practice problems:
1. The masses of H and I atoms are 1.008 amu and 126.904 amu, respectively, where 1
amu = 1.660 x 10-27 kg. The force constant for HI molecule in the gas phase is 314 N.m-1.
The transition frequency for the vibrational transition from the v = 1 to v = 2 state is
________.

2. The frequency of the O-H stretching vibration in CH3OH is 3300 cm-1. The estimated
shift in O-D stretching frequency for CH3OD is _________.

3. The vibrational transition frequency of a diatomic molecule is 2143 cm-1. If the reduced
mass of the molecule is 1.138 x 10-26 kg, the force constant for the bond is __________.
1. The masses of H and I atoms are 1.008 amu and 126.904 amu, respectively, where 1 amu = 1.660 x 10-27 kg. The
force constant for HI molecule in the gas phase is 314 N.m-1. The transition frequency for the vibrational transition
from the v = 1 to v = 2 state is ________.
2. The frequency of the O-H stretching vibration in CH3OH is 3300 cm-1. The
estimated shift in O-D stretching frequency for CH3OD is _________.
3. The vibrational transition frequency of a diatomic molecule is 2143 cm-1. If the reduced
mass of the molecule is 1.138 x 10-26 kg, the force constant for the bond is __________.
Functional group region
IR absorption peaks
• Position: wave number or
frequency: stronger bond –higher
frequency

• Intensity: low intense or high

• Sharpness: broad or sharp