IR SPECTROSCOPY

Content :

✓Introduction

✓Principle

✓Molecular Vibrations (Theory)

✓Factors affecting molecular vibrations

✓IR Spectrum regions

✓Instrumentation
 Spectroscopy

• Spectroscopy is the branch of science that deals with the study of

electromagnetic radiation with molecules or atoms which helps in the
determination of structure of the compound.

• The most important consequence of such interaction is that energy is absorbed or

emitted by the matter in discrete amount called quanta.

• Molecular spectroscopy is based on UV visible and IR which is widely used for

the identification and determination of many organic , inorganic and biochemical
species.

• IR is a powerful tool for determining the structure of both organic and inorganic
compounds.
 Introduction to IR spectroscopy

• Infrared spectroscopy is an important analytical technique for

determining the structure of both inorganic & organic compounds.

• It is also known as vibrational spectroscopy

• IR spectra mainly used in structure elucidation to determine the

functional groups.

• The IR region of electromagnetic spectrum extends from the red of

visible spectrum to the microwave region of electromagnetic
spectrum.
• (IR) spectroscopy deals with the absorption of radiation in the
infrared region of the electromagnetic spectrum.

• IR spectrum gives sufficient information about the structure

(identification of functional groups) of a compound and can also be
used as analytical tool to assess the purity of a compound.

• IR spectroscopy provides spectrum with a large number of

absorption bands and hence provide plenty of information about the
structure of a compound.

• Different bands present in the spectra correspond to various

functional groups and bonds present in the molecule.
• IR spectroscopy covers the range of electromagnetic spectrum 0.8 micron to 200
micron.

• The absorption of IR radiation can be expressed in the terms of wavenumber

(reciprocal of wave length). Which have the unit cm-1.
• IR spectroscopy is broadly classified into three regions :

Region Wavelength range (µ) Wavenumber range (cm-1)

Near 0.8 - 2.5 14000 – 4000

Middle 2.5 – 25 4000 – 667
Group frequency region 4000 – 1500
Finger print region 1500 – 667
Far 25 -200 667 – 50
 Principle of IR spectroscopy

• The principle of IR Spectroscopy is related to the vibrational and rotational

energy of a molecule.

• Molecules are made up of atoms linked by chemical bonds. The movement of

atoms and chemical bonds are like spring and balls(vibration) and this
characteristic vibration are called natural frequency of vibration.

• When the frequency of the IR radiation is equal to the natural frequency of

vibration , the molecule absorbs IR radiation.
• Absorption of IR radiations causes an excitation of molecule from a lower to
higher vibrational level. Each vibrational level is associated with a number of
closely placed rotational levels. Therefore IR Spectroscopy is also called as
“Vibrational –rotational spectroscopy.”

• As the molecules of the compound absorb radiations, they giving rise to

closely packed absorption bands, called IR absorption spectrum.

• The bands correspond to the characteristic functional groups and the

bonds present in a chemical substances. Thus, an IR spectrum of a
compound is considered as the finger print for its chemical
identification.
• All the bonds in a molecule are not capable of absorbing infra-red
energy.

• Criteria for a compound to absorb IR radiation

• 1. Correct wavelength of radiation

• 2. Change in dipole moment

1. Correct wavelength of radiation:

• A molecule to absorb IR radiation, the natural frequency of vibrations of

some part of a molecule is the same as the frequency of incident
radiation.

2. Change in dipole moment

• A molecule is said to have an electric dipole when there is a slight

positive and a slight negative charge on its component of atoms.

• A molecule can only absorb IR radiation when its absorption cause a

change in its electric dipole.
 THEORY OF IR SPECTROSCOPY

• Molecules are made up of atoms linked by chemical bonds.

• A molecule in its ground state posses 3 energy levels, Electronic,

Vibrational and Rotational energy level.

• Absorption in the IR regions is due to the changes in the vibrational and

rotational levels.

• When an electron absorbs less energy, rotational transitions takes place.

• The spectrum observed is called rotational spectrum observed in far IR

region (25 to 300- 400u).
• When the electrons absorbs still higher energy, vibrational transitions
take place which is accompanied with rotational transitions. The spectrum
observed is called vibrational rotational spectrum obtained in middle IR
region (2.5 to 25 u).

• Electronic transitions take place at higher energies, these are not seen in IR.

• This characteristic vibration is called Natural frequency of vibration. The

energy of molecular vibration is quantized.

• When energy in the form of infrared radiation is applied then it causes the
vibration between the atoms of the molecules & when, Applied infrared
frequency= Natural frequency of vibration Then, absorption of IR radiation
takes place & a peak is observed.
• Different functional groups absorb characteristic frequencies of
IR radiation. Hence gives the characteristic peak value.

• Therefore, IR spectrum of a chemical substance is a finger print

of a molecule for its identification.
 Molecular vibrations
• Any change in shape of the molecule like stretching of bonds , bending of bonds or internal
rotation around single bonds refers to vibration in a molecule.
• There are two types of vibrations .
1. Fundamental vibrations: Vibrations which appear as band in the
spectra.
• They are subdivided into two types:
a) Stretching vibrations :
b) Bending vibrations :

a) Stretching vibrations : They involve movement of atom within the

same bond axis such that the bond length changes without any
change in bond angle in regular interval.
• In this type of vibrations the bond length is altered i.e increased or
decreased periodically at regular intervals.
• Stretching vibrations are of two types :

a) Symmetrical stretching

b)Asymmetrical stretching

a) Symmetrical stretching: The atoms of a molecule either move away or

towards the central atom, but in the same direction. The two bond length
increase or decrease. Symmetrical molecules like O=C=O are not IR active
because no change in dipole moment is observed upon stretching vibrations.
b) Asymmetric Stretching: In this type of vibration one atom approach
towards the central atom while other departs from it. One bond length
increase and one bond length decrease.
 BENDING OR DEFORMING VIBRATIONS

• These are the vibrations or oscillation not along the line of bond.

• They involve movement of atoms which are attached to a common central atom,
such that there is change in bond axis and bond angle of each individual atom
without change in their bond lengths.

• Bending vibrations generally requires less energy and occur at longer

wavelength (lower cm-1.) than stretching vibrations.
Types of bending vibrations

I) In-plane bending : In these vibrations there is change in

bond angle ,bending of bonds take place within the same
plane.

a) Scissoring : Occurs when two atoms move back and

forth towards each other i.e approach each other which
leads to decrease in bond angles.

b) Rocking : In these plane bending of atoms occurs

wherein they swing back and forth with respect to the
central atom. In which bond angle is maintained.
2) Out-plane bending : In these vibrations, bending of

bonds takes place outside the plane of the molecule .

a) Wagging : Two atoms move to one side of the

plane. They move up and down the plane.

b) Twisting : one atom moves above the plane and

another atom moves below the plane.

Non fundamental Vibrations
❖ Overtones :

• Overtones are spectral bands that occur when a

molecule transitions to a higher vibrational
energy level. They are multiples of the
fundamental absorption frequency.
• Overtones occur when a vibrational mode is
excited from v=0 to v=2 (the first overtone) or
v=0 to v=3 (the second overtone).
• Overtone peaks are typically much weaker in
intensity compared to the fundamental peaks
because the probability of a transition to a higher
vibrational state is significantly lower.
• Combination bands :

• A combination band appears in an IR spectrum when two or more

molecular vibrations are simultaneously excited by the infrared
radiation, essentially "adding" the frequencies of those vibrations
together to produce a new absorption peak at a higher energy
level than either individual vibration.
2. Fermi Resonance:

• The Fermi resonance effect usually leads to two bands appearing close
together when only one is expected.

• When a fundamental vibration couples with an overtone or combination band,

the coupled vibration is called Fermi resonance.

• As a result, two strong bands are observed in the spectrum, instead of the
expected strong and weak bands. Fermi resonance is often observed in
carbonyl compounds.

• When an overtone or combination band has the same frequency or a similar

frequency to a fundamental , two bands appear , split either side of the expected
value and are of about equal intensity.
 Vibrational frequency
• It occurs when atoms are in periodic. The frequency of the periodic motion is
known as a vibration frequency. The value of stretching vibrational frequency of
bond can be calculated by Hooke's law.

• According to Hooke's law , the stretching frequency is related to the masses of

the atom and the force constant ( a measure of resistance of a bond to
stretching) .

• Where , µ= reduced mass

= Frequency in a cm-1

k = force constant/Strength of bond

C = Velocity of light .
• The amount of energy required to stretch a bond depends on the strength of the
bond and masses of the bonded atoms.

• The force constants for triple bond are three times those of single bonds,
whereas the force constants for double bonds are twice those if single bonds.

• One is that stronger bonds have a larger force constant K and vibrate at higher
frequencies than weaker bonds.

• In general, triple bonds are stronger than double or single bonds between the
same two atoms and have higher frequencies of vibration (higher wave number).
• Reduced mass:

• As the atom bonded to carbon increase in mass, the reduced mass (µ)
increases and the frequency of vibration decreases (wave numbers
gets smaller).

Decreasing K

• Thus the value of absorption frequency of a bond increases with

increasing the bond strength and decreasing the reduced mass of the
bonded atoms.
❖ Hybridization affects :

• Hybridization affects the force constant K, also bonds are

stronger in the order sp > sp2> sp3, and the observed frequencies
of C—H vibration illustrate this nicely.
 Factors influencing vibrational frequency

• There are number of factors that influence the precise frequency

of a molecular vibration namely.

1. Coupling interaction/Vibration

2. Fermi resonance

3. Hydrogen Bonding

4. Electronic effects
 Symmetric stretching
ASymmetric stretching
of C=O at 1760cm-1
of C=O at 1820cm-1
2. Fermi Resonance:

• The Fermi resonance effect usually leads to two bands appearing close together
when only one is expected.

• When a fundamental vibration couples with an overtone or combination band,

the coupled vibration is called Fermi resonance.

• As a result, two strong bands are observed in the spectrum, instead of the
expected strong and weak bands. Fermi resonance is often observed in
carbonyl compounds.

• When an overtone or combination band has the same frequency or a similar

frequency to a fundamental , two bands appear , split either side of the expected
value and are of about equal intensity.
• Eg : CO2,It normally shows fundamental band at 1337cm-1 and
overtone at 1334.6cm-1. But due to the effect of Fermi resonance the
first band shift towards higher frequency and give rise to two bands at
1285.5cm-1and 1388.3cm-1.
3. Hydrogen bonding :
• The presence of hydrogen bonding in the molecule changes the absorption
frequency as well as shape of absorption band.

• Stronger the hydrogen bonding, greater the absorption shift towards lower wave
number from normal value.

• The two types of hydrogen bonding (intramolecular and intermolecular) can be

distinguished by the use of infrared spectroscopy.

• Intermolecular hydrogen bonding is concentration dependent and the

absorption band shift on dilution. The intensities of such bands decrease and
finally disappear. The intermolecular bonding gives rise to broad bands.

• On the other hand intramolecular H-bonding is concentration independent and

are sharp and well defined.
• Eg : Amines show N-H structure at 3500cm-1 in dilute solution, while in
condensed phase spectra absorption takes place at 3300cm-1.

• Alcohol exhibiting intermolecular H-bonding absorbs between 3400-

3200cm-1 , while O-H structure in free alcohols absorbs near 3600cm-1
4. Electronic effects:

• The electronic effect including inductive effect, mesomeric effect, field

effect can cause changes in force constant or bond strength which leads to

the shift in absorption frequency from the normal value.

✓ Inductive effect

✓ Mesomeric effect

✓ Field effect
❖ Field effects :

• In ortho substituted compounds , the lone pair of electrons on two atoms

influence each other through space interactions and change the vibrational
frequencies of both the groups . This effects is known as field effect.

• The non-bonding electrons present on oxygen atom and halogen atom

cause electrostatic repulsions.

• This results in change in the state of hybridisation of C=O groups and

conjugation is diminished and absorption occurs at a higher wave number.

• Thus for such substituted compounds , cis-isomer absorbs at a higher

frequency (field effect) than the trans isomer.
 IR Spectrum region

1. Near Infrared Region between 14000-4000cm-1 :

• (NIRS) allows the study of overtones and harmonic or combination

vibrations.

• Bands in the near infrared are usually weak in intensity.

• They are often overlapped and hence are less useful than the bands in
mid-infrared region.

• This broad region shows absence or presence of many groups in the

molecule.

• The important groups accounted for include NH, OH , C=C , C=O

,C=N etc .
2. Middle Infrared Region between 4000-400cm-1 :

• The MIRS region is to study the fundamental vibrations and the

rotation-vibration structure of small molecules.

• This region is most useful for the organic chemist since most of the

organic molecules absorb in this region.

• The mid-infrared can be divided into two regions like

• a) Functional group region ( 4000-1500)

• b) Fingerprint region (1500-600)

a) Functional group region ( 4000-1500)

• Most of the functional groups present in organic molecules exhibits absorption

bands in the region hence this is known as functional group.

• It contains relatively few peaks.

• These are typically associated within stretching vibrations of functional groups.

• Vibrating bonds in functional groups absorb energy at a frequency that

corresponds to the vibrational frequency of the bond.
b) Fingerprint region (1500-600) :

• The region from 1500 cm-1 to 600 cm-1 usually contains a very
complicated series of absorption .Thus absorption patterns in this region
are unique for any particular compound that is why this is known as
finger print region.

• Number of bending vibrations are usually more than the number of

stretching vibrations .

• Many compounds shows unique absorption bands in this region and which
is very useful for the identification of compound.
• Ex: propan-1-ol and propan-2-ol
c) Far infrared spectroscopy (FIRS) 400-10 cm-1
• Organometallic and inorganic molecules contain heavy atoms
and have weak bonds, therefore the fundamental vibrations of
these molecules fall in this region.

• This region gives few but sharp bands which can be accounted for
the presence of specific groups.
 IR Spectra interpretation
 In general, the IR spectrum can be split into four regions for interpretation:

1. 4000 − 2500 cm-1: Absorption of single bonds formed by hydrogen and

other elements
e.g. O−H, N−H, C−H
2. 2500 − 2000 cm-1: Absorption of triple bonds
e.g. C≡C, C≡N
3. 2000 − 1500 cm-1:Absorption of double bonds
e.g. C=C, C=O , C=N
4. 1500 − 400 cm-1: This region often consists of many different,
complicated bands. This part of the spectrum is unique to each
compound and is often called the fingerprint region. It is rarely used for
identification of particular functional groups.