UNIT-IV SPECTROSCOPY

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

 UNIT-IV SPECTROSCOPY
AIM OF SPECTROSCOPY: DEFINITION OF SPECTROSCOPY:
 Determination of structure of unknown sample.  It is the study of interaction between electromagnetic
 Molecular structure: Arrangement of elemental radiation (EMR) and sample/matter.
atom in a molecule Or GEOMETRY or SHAPE  Interaction EMR and matter provides the structural
of the molecule. information's.

TECHNIQUES AVAILABLE FOR STRUCTURAL DETERMINATION:

Physical Technique (Spectroscopy method) Chemical Technique
 Without chemical reaction on the sample  By performing chemical reaction
 Fast-technique  Slow-technique
 Less quantity of sample required  More quantity of sample required
 Sample can be recovered  Sample can be recovered
 Absolute structure can be arrived  Tentative structure can be arrived (partial)
 Expensive technique  Cheaper technique

ELECTROMAGNETIC RADIATION (EMR):

 EMR is one form of the energy similar to heat, electricity, work etc.
 EMR associated with oscillating electric and magnetic fields.
 Both electric and magnetic fields are vector (magnitude and direction)
properties.
 Electric and magnetic fields are perpendicular to each other.
 ELECTRONS are having both wave and particle nature; DUAL NATURE
 EMR are also acts as electron-Displays DUAL NATURE.
 Each high energy particles are said to be Photon/Quonta.
Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT
Wave is described with following characteristics: UNIT-IV SPECTROSCOPY
1. Wavelength (λ): 2. Amplitude (A):
 It is the distance between the adjacent  The height of crest or depth of trough.
crest/troughs of the wave.  Smaller amplitude = intensity peak/band is less
 Small wavelength, more energy, more waves  Greater amplitude = intensity is greater.
 Large wavelength, less energy, less waves.  Amplitude is the measure of intensity of
radiation.
E α 1/ λ
Units for λ: Å, nm, mµ, µ, mm, cm, m.
1 Å = 10-8 cm ≡ 10-10 m
1 nm = 10-7 cm ≡ 10-9 m
1 nm ≡ 1 mµ Intensity of radiation decreased, as six
1 µ = 10-4 cm ≡ 10-6 m photons are absorbed by sample/matter
1 nm = 10 Å

3. Velocity (c): 4. Frequency (γ or ᶹ):

 In 1 sec/unit time, distance traveled by wave.  Number of waves passed
 Velocity of EMR is constant through a reference point in
 Light velocity = 3 × 1010 cm ≡ 3 × 10⁸ m space at a given time.

5. Wave Number (ṽ): No. of waves in 1 cm distance. γαṽ γ α 1/ λ = c/ λ

 If wavelength is more, ṽ is less Because of proportionality
between γ α ṽ, these two Units: cycles sec-1 ≡ Hertz (Hz)
ṽ = 1/ λ properties can be used mutually. 1 MHz = 106 Hz ≡ 106 cycle/sec
Unit = cm-1, m-1 Ex: IR = frequency = cm-1

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

EMR UNIT-IV SPECTROSCOPY

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

 UNIT-IV SPECTROSCOPY
Energy is increasing from left to right

Spectroscopy (Based on Nature Radiation)

NMR (Nuclear Optical rotatory UV-VIS IR (infrared) Microwave

magnetic resonance) dispersion spectroscopy Spectroscopy Spectroscopy

ESR (electron spin Photoelectron Raman

resonance) spectroscopy Spectroscopy

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

 UNIT-IV SPECTROSCOPY
Spectroscopy

Absorption spectroscopy Emission spectroscopy

Spectrum recorded by taking characteristics of Radiation released by returning
absorbed radiation by sample. Majority of to lower energy states.
spectroscopy are absorption spectroscopy. Ex: Fluorescence,
Ex: NMR, IR, UV-VIS etc phosphorescence, luminescence

Atomic absorption spectroscopy Molecular absorption spectroscopy

 This class of spectroscopy deals with  Molecular spectroscopy deals with the characteristics
characteristics of atom or element. of the molecule (geometry of the molecule).
 Ex: to learn about the valence and core electron.  Provides structural information of the molecule.
 Binding energies of the valence and core electrons  Ex: rotational, vibrational and electronic spectra are
 Arrangement of valence electrons molecular spectroscopy.

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

 UNIT-IV SPECTROSCOPY
Molecular energies: E2 Vo, Ro
There are 4 types of energies
1. Translation energy (Etr): Movement of particle from one V2

position to other position is space. V1

2. Rotational energy (Er): Energy by virtue of bodily rotation.
E
3. Vibrational energy (Ev): change in distance due to E1 Vo, Ro
movement of atoms in space. “Periodic displacement of
V2
atom from their equilibrium position.”
4. Electronic energy (Eel): Un-ceased movement of electrons. V1

Eo, Vo, Ro
E = (Etr) + (Er) + (Ev) + (Eel)
Within single electronic, several rotational and
A molecule can absorb or emit vibrational levels are possible because of
large energy gap.
only in the multiples of Quanta

ΔErotational < ΔEvibrational < ΔEelectronic

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT
 UNIT-IV SPECTROSCOPY
Selection rule:
“Permitted transitions of particles among quantized energy levels or
within quantized energy levels” are said to be selection rule.
Restricting the energy of transition from one state to other.

light

E n
300 nm

X
210 nm

 Transition probability = 0 = Forbidden transition  Allowed transition peaks or bands more

 Transition probability ≠ 0 = Allowed transition intense in spectrum than peaks or bands of
forbidden transitions

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Factors Influencing on the Intensity of Bands/peaks in Spectrum UNIT-IV SPECTROSCOPY
1. Transition probability
E2
2. Population of level/states
EMR
3. Concentration of sample solution
E E1
4. Path length of sample or cell
1 M conc
Eo

Concentration: With increase in conc. Of the sample

solution, the intensity of signal in spectrum increases.
% Intensity α conc of the sample solution

Population: No. of particles accommodated in a quantized level.

 With increase in population, probability of upward transition
increases, more amount of energy absorbed, corresponding
peaks/bands/signal in spectrum appears with more intensity.

Path length (l): By keeping the conc. Of the sample solution

constant, increase in path length increases intensity of the
signal in the spectrum. With increase in path length more
particles interacts with propagating EMR, so more amount
of energy absorbed.
% Intensity α path length, log(Io/I) = A = εcl

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

 UNIT-IV SPECTROSCOPY

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Instrumentation UNIT-IV SPECTROSCOPY

Representation of spectra

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Practical spectroscopy: Factors affecting UNIT-IV SPECTROSCOPY

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Ultraviolet Spectroscopy UNIT-IV SPECTROSCOPY

 UV light can be absorbed by molecules to excite higher energy (most loosely bound)
“electrons” from lower energy states (HOMO) to higher states (LUMO).
 Such transitions can be studied extensively to understand the binding energy of the
corresponding electrons undergoing transition.
 UV-Vis radiation brings about changes in the electronic levels of molecule --- UV-Vis
spectroscopy also referred as “ELECTRONIC SPECTROSCOPY”
 Since π-electrons are most loosely bound in an organic molecule, UV spectroscopy λfar-uv = 10 - 200 nm
λnear-uv = 200 - 400 nm
furnishes a lot of information about the degree of unsaturation in a molecule. λvis = 400 -800 nm
 When the wavelength of the transition exceeds the UV range, based on the same
 Hydrogen/Deuterium lamp
principle, even the colors of molecules can be explained on the basis of absorption of  Tungsten/ halogen lamp
visible light  Sunlight

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

UV-Visible spectroscopy UNIT-IV SPECTROSCOPY
 Sample should have a group capable in absorption Electronic transition
of UV-Vis range of radiation.
 Sample should be with chromophore. Ex. Carbonyl
group.
 If sample is transparent for UV-Vis range of
radiation, does not absorb energy. Ex. Alkanes
 Samples need not be with permanent or induced
dipole moment
 During electronic transition there is a change in the
dipole moment of the molecules.
Representation of UV-VIS Spectrum
 Samples which absorb radiation in visible range
shows color.

Absorption intensity (A)

Or εmax
Or log εmax

λMax
Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT
Beer-Lambert Law UNIT-IV SPECTROSCOPY
Transmittance % Transmittance
𝑰 𝑰
𝑻= 𝑻=
𝑰𝒐 𝑰𝒐

𝑰 𝑰
𝒍𝒐𝒈𝑻 = 𝒍𝒐𝒈 %𝑻 = × 100
𝑰𝒐
𝑰𝒐
%𝑻 𝑰
𝑰𝒐 100 = 𝑰𝒐
𝒍𝒐𝒈𝑻 = − 𝒍𝒐𝒈
Absorb and Molar Absorptivity 2.303 l𝑜𝑔
𝑰𝒐
= α. c. b 𝑰
𝑰 𝒍𝒐𝒈𝑻 = − 𝑨
𝒅𝑰 2.303 𝑰𝒐 𝒍𝒐𝒈𝑻 = − 𝑨
𝒅𝑰 𝑨 = −𝒍𝒐𝒈𝑻
− α cl − = α. c.l α= l𝑜𝑔
𝒅𝒙 𝒅𝒙 c. b(l) 𝑰
𝑻 = 𝟏𝟎 𝑨 𝑰
α 1 𝑰𝒐 𝑨 = − 𝒍𝒐𝒈
𝒃 = l𝑜𝑔 𝑰𝒐
𝑰
𝒅𝑰 2.303 c. b (l) 𝑰 𝑻 = 𝟏𝟎 𝜺.𝒃(𝒍).𝒄
= α.c 𝒅𝒙 %𝑻
𝑰𝒐 𝑰 𝑨 = − 𝒍𝒐𝒈
𝟎 1 𝑰𝒐 𝟏𝟎𝟎
ε= l𝑜𝑔
c. b (l) 𝑰
𝑰
ln = −α. c. b (l) 𝑰𝒐 𝑨 = − 𝒍𝒐𝒈%𝑻 + 𝟐
𝑰𝒐
ε . c . b (l) = l𝑜𝑔 ;
𝑰
𝑰𝒐 𝑰𝒐 𝑨 = 𝟐 − 𝒍𝒐𝒈%𝑻
ln = α . c . b (l) ε . c . b (l) = 𝑨 = l𝑜𝑔
𝑰 𝑰
Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT
 UNIT-IV SPECTROSCOPY

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

UNIT-IV SPECTROSCOPY
Molecular orbitals UNIT-IV SPECTROSCOPY
Linear combination of
Atomic orbitals (LCAO)

ABMO ( *)-Symmetric (gerade)

Anti-bonding Molecular Orbital

BMO ( )-Antisymmetric-(ungerade)
Bonding Molecular Orbital

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Molecular orbitals UNIT-IV SPECTROSCOPY
Linear combination of
Atomic orbitals (LCAO)

ABMO ( *)-Symmetric (gerade)

Anti-bonding Molecular Orbital

BMO ( )-Antisymmetric-(ungerade)
Bonding Molecular Orbital

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Principle Behind UV Spectrometers UNIT-IV SPECTROSCOPY
Relative Energies of Various Orbitals:  These energy gaps are different in different compounds.
 The difference in energy between two orbitals-

 When light passes through a compound, some of its energy promotes an

electron from one of the bonding or non-bonding orbitals to one of the
anti-bonding orbitals.
 The frequency (or wavelength) of absorption depends on the energy gaps
between those two energy levels.

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Principle Behind UV Spectrometers UNIT-IV SPECTROSCOPY
Electronic Transitions  The higher is the energy gap, the lower is the wavelength of the light
absorbed.
 Bigger jumps requires more energy, so absorb light with a shorter
wavelength.

Not all electronic transitions are allowed. Certain restrictions should be

considered for electronic transitions, called “selection rules”

1. The spin quantum number of an electron should not change during the
electronic transition.
2. The transition between two orbitals should be symmetry allowed.

Any transition that violates these rules are called “forbidden transition”. Most common “forbidden transition” is n  π*.

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Principle Behind UV Spectrometers UNIT-IV SPECTROSCOPY

Important Electronic Transitions:

 From π (bonding) orbital to π* (anti-bonding) orbital (π  π*).
 From n (non-bonding) orbital to π* (anti-bonding) orbital (n  π*).
 From n (non-bonding) orbital to σ* (anti-bonding) orbital (n  σ*).

Possible Electronic Transitions: In Alkanes:

1. σ  σ*  σ  σ* or n  σ*
2. (n  σ*)  Usually weak absorptions
3. (σ  π*)
In Alkenes:
4. (n  σ*)
 σ  σ* , σ  π *, π  π *, π  σ *
5. (π  π*)
6. (n  π*)

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Electronic Transitions UNIT-IV SPECTROSCOPY

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Electronic Transitions UNIT-IV SPECTROSCOPY

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Conventions & Terminologies UNIT-IV SPECTROSCOPY
Chromophore:
A covalently unsaturated group responsible for electronic absorption
(e.g., C=C, C=O, aromatic, azo (-N=N-), esters, amides, -NO2 etc.).

Auxochrome:
A saturated group with non-bonded electrons which, when attached to
a chromophore, alters both the wavelength and the intensity of the
absorption (e.g., -OH, -NH2, -NR2 -SH etc.)

Bathochromic Shift:
The shift of absorption to a longer wavelength (also known as “red
shift”).

Hypsochromic Shift:
The shift of absorption to a shorter wavelength (also known as “blue
shift”).

Hyperchromic Effect: An increase in absorption intensity.

Hypochromic Effect: A decrease in absorption intensity.

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Factors effecting position of the band: Solvents & Solutions UNIT-IV SPECTROSCOPY

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

 Solvents & Solutions UNIT-IV SPECTROSCOPY
 The position and intensity of an absorption band may shift if the spectrum was recorded in different solvents.
 Conjugated dienes and aromatic hydrocarbons experience very less “solvent effect”.
 α,β-Unsaturated carbonyls show two different shifts in bands for changing solvents from non-polar to a polar protic one.
 π-π* band moves to longer wavelength, n-π* band moves to
shorter wavelength.
 π* orbitals get stabilized (due to more polarity) by solvation than π
orbitals. n orbitals get stabilized mainly by H-bonding.
Ex: Crotanoldehyde
Solvent λmax π-π* log εmax λmax n-π* log εmax
Iso-octane 214 nm 4.20 329 nm 1.39
Ethanol 220 nm 4.17 322 nm 1.45

Substituent effect
Me
Me

Ex: Acetone & Hexane Ex: Acetone & MeOH Me Me

= 255 = 261 = 268

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Effect of Conjugation UNIT-IV SPECTROSCOPY

In cyclic system a double bond is

forced to stay in s-cis (Cisoid) form,
therefore, shows a red shift with a
drop in intensity.
Probably repulsion between terminal lobes Substitution may force a molecule
of Ψ2 decreases energy of HOMO (Ψ2) in s- to take s-cis form, therefore,
cis form. Hence, less energy (ie. Higher absorbs energy from a longer
wavelength) is required for Ψ2  Ψ3* wavelength (shows a red shift)
transition. than usual s-trans conformer.
Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT
Woodward–Fieser Rules for Diene UNIT-IV SPECTROSCOPY

Woodward (1941) predicted λmax values only for the lowest energy transition (π  π*) from HOMO to LUMO.

Base values:
 Base value for an unsubstituted, conjugated, acyclic/cyclic or hetero-annular diene 214 nm
 Base value for an unsubstituted, conjugated, homo-annular diene 253 nm

Increments for:
 Each extra double bonds in conjugation + 30 nm
 Exocyclic double bond + 5 nm

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Woodward–Fieser Rules for Diene UNIT-IV SPECTROSCOPY

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

 Home-work Woodward-Fieser Rule for Enones UNIT-IV SPECTROSCOPY

Increments for:
Alkyl group/ring residue: α +10
β +12
γ & higher +18
Polar groups: -OH α +35
β +30
δ +50
-OAc: α,β,γ +6
-OMe: α +35
Woodward-Fieser Rule for Enones β +30
Base values: γ +17
Acyclic α,β-unsaturated ketones 215 nm δ +31
6-membered cyclic α,β-unsaturated ketones 215 nm -SR (R = alkyl): β +85
5-membered cyclic α,β-unsaturated ketones 202 nm -Cl: α +15
α,β-unsaturated aldehydes 210 nm β +12
α,β-unsaturated carboxylic acid & esters 195 nm -Br: α +25
Increments for: β +30
Double bond extending conjugation (DEC): +30 -NR2: β +95
Exocyclic double bond: +05
Homo-diene component: +39

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Woodward-Fieser Rule for Enones UNIT-IV SPECTROSCOPY

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Fieser-Kuhn rules for Conjugated Polyenes UNIT-IV SPECTROSCOPY

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Applications of UV-VISIBLE Spectroscopy UNIT-IV SPECTROSCOPY

Qualitative & Quantitative Analysis:

 It is used for characterizing aromatic compounds and conjugated olefins.
 It can be used to find out molar concentration of the solute under study.
Detection of impurities:
 It is one of the important method to detect impurities in organic solvents.
 Detection of isomers are possible.
 Determination of molecular weight using Beer’s law.

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

 UNIT-IV IR SPECTROSCOPY

IR Spectroscopy
The IR Spectroscopic Process
1. The quantum mechanical energy levels observed in IR
spectroscopy are for molecular vibration

2. Matter perceive this vibration as heat

3. Bond length of a covalent bond between two atoms is an

average because the bond is vibrating.

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

The IR Spectroscopic Process
 As a covalent bond oscillates – due to the oscillation of the dipole of the molecule –
a varying electromagnetic field is produced
 The greater the dipole moment change through the vibration, the more intense the
EM field that is generated
 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

IR beam from spectrometer

“coupled” wave

EM oscillating wave
from bond vibration

 The coupled wave now vibrates with twice the amplitude

IR Spectroscopy UNIT-IV SPECTROSCOPY
IR range = 625-4000 cm-1
Requirement: The molecule must be with permanent or
induced dipole moment
“Periodic displacement of nuclei or atoms w.r.t. their
equilibrium positions in a group called Vibration”
Application: Detection of nature of functional groups.
Ex: -OH, -NH2, -C-C, -C=C, -C=O, -C=S, Ar etc

Total no. of Degree of Freedom = 3N, N = no. of atoms

Fundamental vibration for linear molecule = 3N-5
Fundamental vibration for non-linear molecule = 3N-6

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

 The IR Spectroscopic Process UNIT-IV IR SPECTROSCOPY

. There are two types of bond vibration:

• Stretch – Vibration or oscillation along the line of the bond
Symmetric Asymmetric
H H
C C
H H

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

In plane Out of plane (Oops)
H H H H
C C C
C
H H H
H
scissor rock twist wag

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

The vibrations of polyatomic molecules :-Normal modes UNIT-IV IR SPECTROSCOPY

A. Number of vibrational modes or degrees of freedom

 For a molecule composed of N atoms, the total number of coordinates to specify

the locations is 3N (e.g: x, y, z per atom)
 Or we say 3N degrees of freedom
 Translational-3, Rotational (3 for non-linear and 2 for linear molecules)
 The remaining coordinates are directly related to the vibrations between atoms.
 There are 3N-6 degrees of freedom (displacements) of the atoms relative to one
another for a non linear molecule
 There are the 3N-6 independent vibrational modes for non-linear molecules
 3N-5 for linear molecules

For personal use only

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT
Vibrational Modes for H2O (3) UNIT-IV IR SPECTROSCOPY

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Vibrational Modes for CO2 (4)

degenerate
 Regions of Frequencies

Spectral Region Frequency (Hz) Wavenumber (cm-1) Wavelength (, m)

Near -to 3.8 x 1014 to 12800 to 0.78 to 2.5

visible- IR 1.2 x 1014 4000
(NIR)
Combination
bands
Mid Infrared 1.2 x 1014 to 4000 to 200 2.5 to 50
Fundamental 6.0 x 1012
bands for
organic
molecules

Far IR 6.0 x 1012 to 200 to 10 50 to 1000

Inorganics 3.0 x 1011
organometalli
cs
 UNIT-IV IR SPECTROSCOPY

An IR Spectrum in ABSORPTION mode

An IR Spectrum in TRANSMISSION mode

This is the most commonly used representation and the one found in most chemistry and spectroscopy books

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

The IR Spectrum – The detection of different bonds
Infrared band Intensities

• Strong (s) – peak is tall

• Medium (m) – peak is mid-height
• Weak (w) – peak is short

Infrared band shapes

Two of the most common bands are narrow and broad.

 Narrow bands are thin and pointed, like a dagger.
 Broad bands are wide and smoother.
Eg: broad band is that displayed by O-H bonds, such as
those found in alcohols and carboxylic acids,
INFRARED ACTIVE BONDS UNIT-IV IR SPECTROSCOPY

 Not all covalent bonds display bands in the IR spectrum. Only IR active polar bonds display band
 The intensity of the bands depends on the magnitude of the change in dipole moment associated with
the bond in question:
 Strongly polar bonds such as carbonyl groups (C=O) produce strong bands.
 Medium polarity bonds and asymmetric bonds produce medium bands.
 Weakly polar bond and symmetric bonds produce weak or non observable bands.

Symmetric bond that has identical or nearly identical groups on each

end will not absorb in the infrared

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Vibrating diatomic molecule: Simple harmonic oscillator model (SHO) UNIT-IV IR-SPECTROSCOPY
Energy of diatomic molecule
Frequency of stretching vibration of
diatomic molecule ωosc
Every bond has an intrinsic vibrational frequency
 Frequency of bond vibration does not change
with increase in the energy of the system 𝒎𝟏𝒎𝟐
𝝁=
The vibrational frequency depends on 𝒎𝟏 + 𝒎𝟐
 the mass of the system
 the strength of the bond (force constant)
k is the force constant,
 is independent of degree of distortion
μ is the reduced mass

 Force constant is a measure of strength of the bond

 Stronger the bond, higher the force constant and

Hooke’s law :  therefore higher the frequency of vibration

1. Restoring force, f = -kx
k = force constant
x = displacement from equilibrium positions
f = - k (r-req) (r = internuclear distance)
𝟏 𝟐
2. The Energy, 𝑬= 𝒌 𝒓 − 𝒓𝒆𝒒
𝟐
Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT
Energy levels for vibrating diatomic molecule, SHO UNIT-IV IR SPECTROSCOPY
By solving Schrodinger equation, we can get the allowed
vibrational energies for vibrating diatomic molecule:-
𝟏 𝜐 (vibrational quantum number) = 0, 1, 2, 3--------
E𝝊= (𝜐+ 𝟐 )h𝜔𝑜𝑠𝑐 joules
ωosc is the oscillating frequency of a bond vibrating in SHO

IR frequencies are usually expressed in wave number (cm-1) as this is proportional to energy
Energy expressed in spectroscopic unit
𝑬
(wave number in cm-1), 𝜺𝝊= 𝝊
𝒉𝒄
𝟏
𝜺𝝊= (𝜐+ 𝟐 )𝜔𝑜𝑠𝑐 𝑐𝑚−1 --------- Eq 1

Lowest energy for vibrating diatomic molecule, SHO

 A molecule can never have zero vibrational energy.
𝟏 𝟏
E𝝊= (𝜐+ )h𝜔𝑜𝑠𝑐 joules
𝟐 𝝊 𝑜𝑠𝑐
−1  Atoms are never at rest relative to each other.
𝟐  Zero point energy depends only upon the strength of
We can get the minimum energy when υ = 0 chemical bond and atomic masses.

“Zero point energy”

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Lowest energy for vibrating diatomic molecule, SHO UNIT-IV IR-SPECTROSCOPY
𝟏 𝟏
E𝝊= (𝜐+ 𝟐 )h𝜔𝑜𝑠𝑐 joules −1
𝝊 𝟐 𝑜𝑠𝑐

First excited state energy, when υ = 1

𝜺𝝊 → 𝝊 𝟏 = 𝜺𝝊 𝟏 − 𝜺𝝊
Second excited state energy, when υ = 1

Allowed energy levels for vibrating diatomic molecule, SHO

The difference between energy levels expressed in cm-1 directly
Selection rule for a simple harmonic gives the wavenumber of spectral line absorbed or emitted
oscillator undergoing vibrational changes Energy levels of SHO are equally spaced
The separation between adjacent
𝝊=±1
energy levels 𝝊 and 𝝊 +1
Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT
The anharmonic oscillator UNIT-IV IR SPECTROSCOPY

Real molecules do not obey laws of simple harmonic oscillator for large amplitude vibrations

Allowed vibrational energies for

AHO can be obtained by using

E = De [1- {𝒂 𝒓𝒆 𝒓 } ]2

(Morse function)

a = constant for a particular molecule

De = dissociation energy

  2 1/ 2
a   
2hcD
 e 

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

The an-harmonic oscillator: the allowed vibrational levels UNIT-IV IR SPECTROSCOPY

Allowed vibrational energies for a bond (AHO) can be obtained by solving the Schrodinger
equation using Morse function

𝟏 𝟏 𝟐
𝝊 𝒆 𝒆 𝒆
𝟏 ( =1,2,3………)
𝟐 𝟐

𝟏 𝟏
𝝊 𝒆 𝒆 , ; ( =1,2,3………)
𝟐 𝟐

-1
𝒆
𝒆
𝒆

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Comparison of SHO and AHO : UNIT-IV IR SPECTROSCOPY
An-harmonic oscillator: the allowed vibrational levels
𝟏 𝟏
𝜺𝝊 = 𝝊 + 𝟐 𝝎𝒆 𝟏 − 𝒙𝒆 𝝊 + 𝟐 , 𝑐𝑚 ; (𝝊 =1,2,3………)

𝝎𝒆 = vibrational frequency in cm-1𝒙𝒆 = anharmonicity constant

Simple harmonic oscillator: the allowed vibrational levels

𝜺𝝊 = 𝜐 + 𝜔 𝑐𝑚 for SHO -------------------Eq 1

Comparing with the vibrational energies of SHO and AnSHO oscillators i.e Eq 1 and Eq 2

𝝎𝒐𝒔𝒄 = 𝝎𝒆 {1- 𝒙𝒆 𝜐 + } 𝑐𝑚

 An-harmonic oscillator behaves like SHO, but the oscillating frequency decreases
with increasing value of 𝝊

 The energy levels are crowded together at higher values of 𝝊.

 In an-harmonic oscillator the energy levels are not equally spaced,
 Molecule dissociates at largest separation
Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT
The an-harmonic oscillator: the allowed vibrational levels UNIT-IV IR SPECTROSCOPY

𝟏 𝟏
𝜺𝝊 = (𝝊 + )𝝎𝒆 𝟏 − 𝒙𝒆 𝝊 + 𝑐𝑚
𝟐 𝟐

𝝎𝒐𝒔𝒄 = 𝝎𝒆 {1- 𝒙𝒆 𝜐 + } 𝑐𝑚

Zero point energy, for 𝝊 = 0

𝟏 𝟏
 𝟎 = 𝟐 𝝎𝒆 {1- 𝟐 𝒙𝒆 } cm-1 Zero point energy
𝟏 -1
𝝎𝝊 𝟎 = 𝝎𝒆 {1- 𝟐 𝒙𝒆 } cm

F𝐢𝐫𝐬𝐭 𝐞𝐱𝐜𝐢𝐭𝐞𝐝 𝐬𝐭𝐚𝐭𝐞 𝝊 = 1 S𝐞𝐜𝐨𝐧𝐝 𝐞𝐱𝐜𝐢𝐭𝐞𝐝 𝐬𝐭𝐚𝐭𝐞 𝝊 = 2

𝟑 𝟑
 𝟏 = 𝟐 𝝎𝒆 {1- 𝟐 𝒙𝒆 } cm-1 T𝐡𝐢𝐫𝐝 𝐞𝐱𝐜𝐢𝐭𝐞𝐝 𝐬𝐭𝐚𝐭𝐞 𝝊 = 3
𝟑 -1
𝝎𝝊 𝟏 = 𝝎𝒆 {1- 𝟐 𝒙𝒆 } cm

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

The an-harmonic oscillator: the allowed transitions UNIT-IV IR SPECTROSCOPY
The selection rules for an-harmonic oscillator 𝟏 𝟏
𝟐
𝟏
𝜺𝝊 = 𝝊 + 𝝎𝒆 − 𝝊 + 𝝎𝒆 𝒙𝒆 𝒄𝒎
𝟐 𝟐
 = 1, 2 etc
Probable transitions

𝝊 = 0  𝝊 = 1,  𝝊 = 1:
intense absorption (Fundamental absorption)
  =𝝎𝒆 (1- 2 𝒙𝒆 ) cm-1

𝝊 = 0  𝝊 = 2,  𝝊 = 2:
with small intensity (First overtone) 𝝊 = 1  𝝊 = 2,  𝝊 = 1:
  = 2𝝎𝒆 (1- 3𝒙𝒆 ) cm-1 Week absorption (Hot band)
  =? cm-1
𝝊 = 0  𝝊 = 3,  𝝊 = 3:
negligible intensity (Second overtone)

  = 3𝝎𝒆 (1- 4 𝒙𝒆 ) cm-1

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

 UNIT-IV IR SPECTROSCOPY
The equilibrium vibrational frequency of I2 is 215 cm-1, and the anharmonicity constant is 0.003. Compare the intensity
of the hotband (v=1 to v=2) to fundamental band. Justify your answer
𝟏 𝟏
𝝊 𝒆 𝒆 ; ( =1,2,3………)
𝟐 𝟐
𝟏 𝟏
𝜺𝟐 = 𝝎𝒆 𝟏 − 𝒙𝒆 𝟐 + 𝟐 (𝟐 + 𝟐) 𝑐𝑚
𝟓 𝟓 𝝎𝒆 = 215 cm-1
𝜺𝟐 = 𝟐 𝝎𝒆 𝟏 − 𝟐 𝒙𝒆 𝑐𝑚 similarly
𝒙𝒆 = 0.003.
𝟑 𝟑
𝜺𝟏 = 𝟐 𝝎𝒆 𝟏 − 𝟐 𝒙𝒆 𝑐𝑚
  fund =𝝎𝒆 (1- 2 𝒙𝒆 ) cm-1
So,   hot band = 𝝎𝒆 (1- 4 𝒙𝒆 ) cm-1
  fund = 215 (1- 2x0.003) cm-1
So,   hot band = 𝟐𝟏𝟓 (1- 4 x 0.003) cm-1 = 213.71 cm-1
= 212.42 cm-1  E fund= hc   fund band
 E hot= hc   hot band = 4248.127x10-24 J
= 4222. 485 x 10-24 J
=  /
=𝑒  /
=𝑒
4222. 485 x 10−24 J = 0.3584 ≈ 0.36
. x 10−23 JK−1
= 0.3606
 Factors effecting IR frequencies UNIT-IV IR SPECTROSCOPY

1. Force constant
2. Relative masses of the atoms attached to band
3. Inductive effect, hyperconjugation, resonance
4. Strain or steric factor
5. H-bonding
6. Phase changes

 Stronger bonds have a larger force constant K and vibrate at higher frequencies
than weaker bonds.

 Bonds between atoms of higher masses (larger reduced mass) vibrate at lower
frequencies than bonds between lighter atoms.

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

 Factors effecting IR frequencies UNIT-IV IR SPECTROSCOPY

 Bending motions occur at lower energy (lower

frequency) than the typical stretching motions because
of the lower value for the bending force constant K.

 No two molecules will give exactly the same IR

spectrum (except enantiomers)

Enantiomers are mirror images of each other that

 Hybridization affects the force constant K, also sp>sp2>sp3
are non-superimposable (not identical)

 Resonance also affects the strength and length of a

bond and hence its force constant K.

 Thus, a normal ketone has its C=O stretching vibration at 1715 cm−1; a ketone that
is conjugated with a C=C double bond absorbs at a lower frequency, near 1675 to
1680 cm−1
 That is because resonance lengthens the C=O bond distance and gives it
more single-bond character

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT

Factors effecting IR frequencies UNIT-IV IR SPECTROSCOPY
Inductive, Resonance effect: Steric effect:
 Resonance = decreases the vibrational frequencies
 Inductive = Increases the vibrational frequencies

Dr. N. Jothi Lakshmi, Dept. of Chemistry, NITT