[DOCUMENT TITLE]

Physical Chemistry V – reading material only for students at Miranda House, University of Delhi 2021

MOLECULAR SPECTROSCOPY

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Physical Chemistry V – reading material only for students at Miranda House, University of Delhi 2021

Reference books:

1. Physical Chemistry: A Molecular Approach by McQuarrie and Simon

2. Fundamentals of Molecular Spectroscopy by Banwell and McCash
3. Molecular Spectroscopy by Sindhu
4. Quantum Chemistry and Spectroscopy by Engel and Reid
5. Molecular structure and spectroscopy by G Aruldhas
6. Molecular Spectroscopy by Hollas
7. Spectroscopy by Lampman, Pavia, Kriz, Vyvyan
8. Spectroscopic Methods in Organic Chemistry by Williams and Fleming
9. Spectroscopic Identification of Organic Compounds by Silverstein

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Introduction

Spectroscopy can be of two types:

 Atomic
 Molecular.

All forms of spectroscopy involve the interaction of electromagnetic radiation with matter. The
incident radiation interacts with the sample/matter. The transmitted radiation, gives a spectrum
which is analysed to understand various structural details regarding the sample.

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ktopdefault.aspx%2Ftabid-
11913%2F&psig=AOvVaw2oYqti18SueI9KbFA_OzYP&ust=1596197331415000&source=i
mages&cd=vfe&ved=0CAIQjRxqFwoTCLC1y9H49OoCFQAAAAAdAAAAABAK

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Electromagnetic radiation can be considered as a simple harmonic wave travelling in straight

lines except when reflected or refracted. The simple harmonic wave:

has properties of a sinusoidal wave and can be represented as: = sin where the
displacement y has a maximum value A and 0 ≤ ≤ 360˚ or 0 ≤ ≤ 2 radians.

If the angular velocity is ω, then

= radians where t is time. Substituting for θ in the above equation: = sin . If the
frequency associated with this sinusoidal waveform is ν, then = 2 ..
Therefore = sin 2 .

The wavelength λ associated with the sinusoidal waveform is = / , where c is the velocity
of light. Units of λ are usually in nm (= 10-9m).

The wavenumber, = . The units of are either m-1 or cm-1.

A molecule is a collection of positively charged atomic nuclei surrounded by a cloud of

negatively charged electrons. Its stability results from a balance among the attractive and
repulsive forces of the nuclei and electrons. A molecule is characterized by the total energy
resulting from these interacting forces. As is the case with atoms, the allowed energy states of
a molecule are quantized. Molecular spectra result from either the absorption or the emission
of electromagnetic radiation as molecules undergo changes from one quantized energy state to
another. The mechanisms involved are similar to those observed for atoms but are more
complicated. The additional complexities are due to interactions of the various nuclei with each
other and with the electrons, phenomena which do not exist in single atoms. In order to analyse
molecular spectra it is necessary to consider simultaneously the effects of all the contributions
from the different types of molecular motions and energies.

There are two primary sets of interactions that contribute to observed molecular spectra. The
first involves the internal motions of the nuclear framework of the molecule and the attractive

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and repulsive forces among the nuclei and electrons. The other encompasses the interactions
of nuclear magnetic and electrostatic moments with the electrons and with each other.

The first set of interactions can be divided into the three categories given here in decreasing
order of magnitude: electronic, vibrational, and rotational. The electrons in a molecule
possess kinetic energy due to their motions and potential energy arising from their attraction
by the positive nuclei and their mutual repulsion. These two energy factors, along with the
potential energy due to the mutual electrostatic repulsion of the positive nuclei, constitute the
electronic energy of a molecule. Molecules are not rigid structures, and the motion of the nuclei
within the molecular framework gives rise to vibrational energy levels. In the gas phase, where
they are widely separated relative to their size, molecules can undergo free rotation and as a
result possess quantized amounts of rotational energy. In theory, the translational energy of
molecules through space is also quantized, but in practice the quantum effects are so small that
they are not observable, and the motion appears continuous. The interaction of electromagnetic
radiation with these molecular energy levels constitutes the basis for electron spectroscopy,
visible, infrared (IR) and ultraviolet (UV) spectroscopies, Raman spectroscopy, and gas-phase
microwave spectroscopy.

The second set of molecular interactions form the basis for nuclear magnetic resonance
(NMR) spectroscopy, electron spin resonance (ESR) spectroscopy.

Molecular spectra are observed when a molecule undergoes the absorption or emission of
electromagnetic radiation with a resulting increase or decrease in energy. There are limitations,
imposed by the laws of quantum mechanics, as to which pairs of energy levels can participate
in energy changes and as to the extent of the radiation absorbed or emitted. The first condition
for the absorption of electromagnetic radiation by a molecule undergoing a transition from a
lower energy state, , to a higher energy state, , is that the frequency of the absorbed
radiation must be related to the change in energy:
∆ = − = ℎ , where is the radiation frequency and h is Planck’s constant.

E1

∆E

E0

Conversely, the application of electromagnetic radiation of frequency to a molecule in energy

state can result in the emission of additional radiation of frequency as the molecule
undergoes a transition to state . These two phenomena are referred to as induced absorption
and induced emission, respectively. Also a molecule in an excited (high) energy state can

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spontaneously emit electromagnetic radiation, returning to some lower energy level without
the presence of inducing radiation.

https://www.britannica.com/science/spectroscopy/Molecular-spectroscopy

Electromagnetic radiation is conventionally divided into a number of distinct regions, each of

which covers a range of energies that corresponds to a different type of molecular process. In
order of increasing frequency these are:

 Radiofrequency or Rf (3 x 106 to 3 x 1010 Hz): ∆E due to the change in the direction

of spin of a nucleus (nuclear magnetic resonance, NMR).
 Microwave (3 x 1010 to 3 x 1012 Hz): ∆E due to the change in the direction of electron
spin (electron paramagnetic resonance, EPR, also known as electron spin resonance,
ESR) and the separations between rotational energy levels of gaseous molecules.
 Infrared or IR (3 x 1012 to 3 x 1014 Hz): ∆E due to the transitions between vibrational
energy levels. Raman spectroscopy also uses IR radiation.
 Visible and ultraviolet or UV (3 x 1014 to 3 x 1016 Hz): ∆E corresponds to the
separations between the energy levels of valence electrons, e.g. a transition from the
HOMO to the LUMO.
 X-ray (3 x 1016 to 3 x 1018 Hz): ∆E corresponds to the change of the electron
distribution involving the inner electrons.
 γ –ray (3 x 1018 to 3 x 1020 Hz): ∆E corresponds to the rearrangement of nuclear
particles.

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https://www.google.com/url?sa=i&url=https%3A%2F%2Ffanyv88.com%3A443%2Fhttps%2Fwww.differencebetween.c
om%2Fdifference-between-atomic-spectroscopy-and-molecular-
spectroscopy%2F&psig=AOvVaw05Q9vsWoAC3mYblwD9bJeA&ust=1596262392
641000&source=images&cd=vfe&ved=0CAIQjRxqFwoTCMD0kf7q9uoCFQAAAA
AdAAAAABAD

In general all spectrometers consist of

 a transmitter which is the source of the electromagnetic radiation

 a sample cell/holder
 a detector
 signal/spectrum to be recorded

Transmitter Sample Detector Signal/recorder

If the sample interacts with the incident radiation there is an exchange of energy between the
sample and the transmitted radiation. The radiation detected by the detector will then be
different from the incident radiation. The detector compares the two types of radiation and the
change is reflected in the signal which is recorded in the form of a spectrum. Interpretation of
this spectrum gives information regarding the structure of the molecule/sample. The incident
electromagnetic radiation has both an electric vector and a magnetic vector. For this radiation
to be able to interact with the sample, the sample must have either electrical or magnetic
properties.

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Microwave or Rotational Spectroscopy
Microwave or rotational spectroscopy uses microwave radiation to measure the energies of
rotational transitions for molecules in the gas phase. It accomplishes this through the interaction
of the electric dipole moment of the molecules with the electromagnetic field of the exciting
microwave photon. To enable this interaction, the sample must have a permanent dipole
moment.

https://slideplayer.com/slide/6169345/18/images/10/Microwave+Spectroscopy.jpg

This spectroscopy utilizes photons in the microwave range to cause transitions between the
quantized rotational energy levels of a gas molecule. The sample must be in the gas phase and
cannot be in the liquid or solid phase. The intermolecular interactions hinder the rotational
motion in the liquid and solid phases of the molecule. Rotational motion is defined as motion
about the centre of gravity (CG) of the molecule/sample. Rotational motion can be resolved
along three perpendicular axes through the CG - the rotational axis is defined as the axis
passing through the CG. If the three mutually perpendicular axes are defined in general as A,
B and C the moment of inertia, I will have three components along these three axes – IA, IB and
IC.

For microwave spectroscopy, molecules can be broken down into five categories based on their
shape and the moment of inertia around the three orthogonal rotational axes. These five
categories include diatomic molecules, polyatomic molecules - linear and non-linear
molecules, spherical tops, symmetric tops and asymmetric tops.

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Physical Chemistry V – reading material only for students at Miranda House, University of Delhi 2021

Classification of molecules:

 Linear molecules: in these molecules rotation can be:

(i) About the bond axis – if the internuclear axis is designated A, then the resulting
moment of inertia is IA.
(ii) End-over-end in the plane of the paper – if the axis perpendicular to the
internuclear axis in the plane of the paper is designated B, then the resulting
moment of inertia is IB
(iii) End-over-end perpendicular to the plane of the paper – if the axis perpendicular
to the inetrnuclear axis and perpendicular to the plane of the paper is designated
C, then the resulting moment of inertia is IC.

For linear molecules, IB = IC and IA is negligible. Examples are O-C-S, H-Cl etc.

 Symmetric top molecules: here again IB = IC but IA ≠ 0. Example : CH3F

 Spherical top molecules: here IA = IB = IC. Example : CH4
 Asymmetric top molecules: here ≠ ≠ .

In this course we are studying only linear molecules.

Diatomic molecules:

As the diatomic molecule rotates about its centre of gravity (CG) the dipole moment of the
molecule changes its direction and follows a pattern similar to the incident sinusoidal
electromagnetic radiation. This implies that as the molecule rotates the dipole changes in a
periodic manner. For example, if the arrow head represents the direction of the dipole then the
component of the dipole along any one specified direction follows a crest, zero, trough, zero,
crest and so on.

The molecules are studied within the rigid rotator approximation. This implies that as the
molecule rotates, the bond behaves like a rigid rod, i.e. there is no change in the internuclear
distance.

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A B

CG O
Consider a heteronuclear diatomic molecule AB where the atomic masses are mA and mB and
whose CG is at O. Let the internuclear distance be ro and let the distance between atom A and
the CG be rA and that between atom B and the CG be rB.

Then = +

Taking moments about the CG:

Moment of inertia, = + = + = +

=( + )

Also, = = ( − )= −

Therefore, = ( )
. Similarly = ( )

Hence = ( )
= μ , where the reduced mass of the molecule μ = ( )
.

To evaluate the energy associated with the molecule AB undergoing rotational motion, the
relevant Schrodinger’s equation needs to be set up and evaluated. This requires setting up the
Hamiltonian for the molecule AB rotating under rigid rotator approximation. Rotational motion
implies movement about the centre of gravity. The internuclear distance, , is fixed within the
rigid rotator approximation, hence the potential energy will remain constant during the motion.
Assuming this constant potential energy to be zero, ( ) = 0. The rotational energy will then
entirely depend on kinetic energy.

Following the classical mechanical approach:

= + = +0 = ; where is the linear velocity.

In terms of the angular velocity, ω, = . Hence:

= = ( )= .

The moment of inertia, I = , where L is the angular momentum.

Hence, = .

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From the above, = = =

For the quantum mechanical approach, the operator corresponding to the observable is
required. Since the operator corresponding to the observable is known, the Hamiltonian
operator, Ĥ, corresponding to is .

In the polar coordinate system discussed earlier,

1 1
= −ℏ +

Also the Laplacian operator in the polar coordinate system is:

1 1 1
∇ = + +

= ( ) + + .

Since the internuclear distance is constant the ∇ operator will be a function only of the angles
θ and . Hence:

∇ = + .

Comparing the RHS of the expressions for and ∇ :

∇ = (− ℏ )

or = −ℏ ∇

Substituting in the expression for the Hamiltonian operator:

ℏ
Ĥ≡ (−ℏ ∇ ) =- ∇

The corresponding Schrodinger equation is: Ĥ = ; where ψ is a function of the

variables (angles) θ and . Hence:
ℏ
− ∇ ( , )= ( , ).

The solution to the above Schrodinger’s equation gives the expression for and ( , ).

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The rotational energy levels are quantized and take a specific/discrete value depending on the
value of the rotational quantum number J. Hence or or ( )is:

= ( + ) in units of Joules (J).

ħ
= ( + ) in units of Joules (J).

The wavefunction ( , ) is associated with the quantum numbers and . The values of
are 0,1,2,3….. and those of are ± , ±( − 1), ±( − 2) … .0. Hence can take (2 + 1)
distinct values for every value of . The value of = 0 corresponds to the rotational ground
state where the rotational energy is zero, i.e. there is no rotational motion.

The wavefunction ( , ) has mathematical expressions corresponding to the values of the

quantum numbers and . Hence it is expressed as , ( , ). The mathematical
expressions for some values of J and mJ are:

Value of J Value of mJ , ( , ).

0 0 1
√2

1 0 √6
cos
2√2

1 +1 √
exp( ) sin
√

1 -1 √
exp(− ) sin
√

In units of wavenumber (cm-1), the rotational energy, εJ is:

ℎ 1 ℎ
= = ( + 1) = ( + 1) = ( + );
ℎ 8 ℎ 8

Where the rotational constant, =

If = 0, there is no rotational energy or there is no rotational motion associated with the

molecule AB.

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The rotational transitions which are allowed follow the selection rule ∆ = ±1. This implies
that the transition probability for a transition from the rotational level to the rotational level
( + 1) is non-zero, i.e.

∫ ( , ) ( , ) ≠ 0 OR ∫ ( , ) ( , ) ≠0

Hence the change in energy due to the transition is:

∆ = ( ) −

In general, if the higher rotational level is and the lower rotational level is ′ then the change
energy ∆ε is:
-1
Rotational " /cm Rotational /cm-1 Change in energy ,
quantum quantum ∆ε/cm-1
number ′ number

0 0 1 2B 2B

1 2B 2 6B 4B

2 6B 3 12B 6B

3 12B 4 20B 8B

′ B { ′ ( ′+1)} = ( ′+1) B {( ′+1)( ′ +2)} 2B ( ′+1)

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A schematic energy level diagram and the corresponding rotational/microwave spectrum is

shown below:

https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Ma
ps/Supplemental_Modules_(Physical_and_Theoretical_Chemistry)/Spectroscopy/Rotational_
Spectroscopy/Microwave_Rotational_Spectroscopy

As is evident from the above spectrum, the rotational/microwave spectrum for any diatomic
molecule will consist of a series of lines; the separation between successive lines in the
spectrum is 2B cm-1. Analysis of the spectrum will give a value of the rotational constant, B
from which the internuclear distance can be evaluated if the reduced mass μ is known.

It may be noted that the x-axis of a rotational/microwave spectrum could have units of cm-1,
m-1, or Hz.

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Intensity of the spectral lines:

The intensity of the spectral lines is related to the transition probability, i.e. the relative
probability of the transition occurring. In terms of an integral, the transition probability can be
expressed as: ∫ ” . In the present context, the operator would represent the
rotational transition. Calculations have shown that the transition probability is practically the
same for all ∆ = ±1 transitions. However, the intensity of the spectral lines varies. This
variation arises because the population of the rotational levels, which governs the intensity,
depends on the rotational quantum number.

The population of the rotational levels depends upon two contributing factors – Boltzmann
distribution and degeneracy of the rotational level.

1. Boltzmann distribution:
For = 0 the rotational energy = 0.
Let the population of this lowest rotational level ( = 0) be .
Let the population of any higher rotational energy level J be .
Following Boltzmann distribution, the ratio of the population of the higher rotational
level to that of the ground rotational level at a temperature T is:
∆ ( − ) ℎ ( + 1)
= {− }= {− } = exp − = exp{− }

This equation implies that the ratio will exponentially decay as J increases. Hence
the population of the rotational level decreases as J increases.

A typical exponential decay for the equality above is:

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2. Degeneracy of the rotational level:

For a diatomic rotator whose moment of inertia is I and rotational frequency is ω, the
rotational energy from classical mechanics is given by:
=
The angular momentum, ⃗ = Iω. Therefore, 2 = .
Hence ⃗ = 2 or ⃗ = (2 )
From the quantum mechanical treatment, = ( + 1). Substituting this
expression in the RHS of ⃗,
⃗= ( + 1) in units of ћ.
Since the angular momentum is quantized it can only take specific directions such that
its component along a reference direction (usually the z-direction) is either zero or an
integral multiple of units of ћ.

https://encrypted-
tbn0.gstatic.com/images?q=tbn%3AANd9GcR0eHJdbJ_ntyfuvsSctSNsaaSI9n8JLbZ
F7g&usqp=CAU

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The magnitude of the angular momentum for all these permitted directions will always be the
same, i.e. ( + 1) in units of ћ.
For example:
If J = 1, ⃗ = √2 in units of ћ. Or ⃗ = 1.414 in units of ћ.
The directions permitted for this angular momentum vector will be such that its component
= ±1, 0; the values of Jz identify with . This implies that the rotational level = 1 has
three-fold degeneracy.
In general the rotational level J will have a degeneracy of (2 + 1). Hence as increases the
degeneracy also increases. If degeneracy increases the population will also increase.

The two contributing factors mentioned above are such that as increases one factor causes a
decrease in population while the other causes an increase in population. Combining the two
factors:
( )
(2 + 1) exp{− }
( )
or =( ) (2 + 1) exp{− }
( )
or = ( ) (2 + 1) exp{− }
( )
or = ( )′ (2 + 1) exp{− }
Since the factors are such that one causes an increase and one causes a decrease, will
increase to a maximum and then decrease. At the point of maxima, = 0.
( )
Evaluating ( )′(2 + 1) exp{− } and setting it equal to zero an
expression is obtained for that rotational level which has maximum population. This
rotational level is given the symbol .
( )
( )′(2 + 1) exp{− }

( ) ( )
= 2 exp − +2J ( )(2 + 1) exp −

( )
+( )(2 + 1) exp{− }.

Equating this to zero, 2 + 2J (2 + 1) + (2 + 1) = 0

Or, − + 2 (2 + 1) + (2 + 1) = 0

2
=4 + 4 + 1 = (2 + 1)
ℎ

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2
= (2 + 1)
ℎ

2
−1=2
ℎ

Or = − .

Jmax is defined as the value of the rotational quantum number corresponding to the rotational
level with the maximum population. If the value of B is known and the temperature T is also
known then the value of Jmax can be calculated. The value so calculated would usually not be
an integer. However, the value of Jmax must be an integer, hence the value reported for Jmax
should be the lower integer. For example if the calculations result in a value of Jmax = 18.78,
the value of Jmax to be reported is 18.

A typical plot of the relative population as a function of the rotational quantum number, J is:

https://upload.wikimedia.org/wikipedia/en/thumb/6/64/Populations_of_rotational_sta
tes.png/220px-Populations_of_rotational_states.png

This implies that the intensity will vary, in the same way as the population. The transition
originating in the rotational level with maximum population, will be the most intense.

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A typical rotational/microwave spectrum for the 12C16O molecule is:

https://www.researchgate.net/profile/David_Naylor/publication/253391065/figure/fig
10/AS:637396660023300@1528978614890/The-rotational-spectrum-of-CO-The-
line-intensities-are-for-a-temperature-of-296-K-The.png
Analyse this spectrum and evaluate the rotational constant B and the internuclear
distance for the carbon monoxide molecule.

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Problem:
1 35
H Cl shows the rotational transitions characteristic of diatomic molecules. Using the
data given below:
(a) Calculate the value of the rotational constant, B and the internuclear distance, r0.
(b) If the temperature of the sample is 300K, calculate Jmax

υ cm-1 J -> J+1

83.03 3-4

103.73 4-5

124.3 5-6

145.03 6-7

165.51 7-8

185.86 8-9

206.38 9-10

226.5 10-11

_____________________________________________________________________

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Effect of isotopic substitution:

Isotopic substitution changes the reduced mass, μ, of the molecule. Within the rigid rotator
approximation, if it is assumed that isotopic substitution does not change the internuclear
distance, , then the change in the value of the rotational constant, B will be only due to the
change in the reduced mass.

Consider the molecules: 12C16O and the isotpically substituted 13C16O.

Let the rotational constant for 12C16O be and the corresponding reduced mass ′.
Similarly, let the rotational constant for 13C16O be " and the corresponding reduced mass ".
If the internuclear distance for both these molecules is , i.e. remains unchanged, then:

"
= = cm-1 and = = cm-1
"

"
The ratio = .

Also, since " > ′, the rotational constants will be > ".

If the sample consists of a mixture of the two isotopically substituted species then the
rotational/microwave spectrum will consists of two sets of equally spaced lines. One set
corresponding to the presence of 12C16O wherein the separation between successive lines will
be 2 and the other set corresponding to the presence of 13C16O wherein the separation
between successive lines will be 2 . As the difference between and is small the lines
at 2 and 2 will appear close together. If the lines need to be clearly resolved the
spectrometer/instrument will need to have a minimum resolution which is ≥ ( − "). The
relative intensity of the lines appearing at 2B’ and 2B” will give an estimate of the abundance
of the isotopically substituted species.

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The figure below shows the theoretical stick line spectrum of the two molecules 12C16O and
13 16
C O. A change in the reduced mass, µ, causes a change in the value of the rotational constant,
B, and hence the spacing between two successive lines, 2B, changes.

https://ifasonline.com/theme/images/ChemicalScience/topic56_image7.png

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Triatomic linear molecules:

These could be either bent or linear. Here only linear molecules are being considered and these
are being considered within the rigid rotator approximation. This implies that there is no change
in the internuclear distances.

The major differences as compared to diatomic molecules are:

 Since the moment of inertia here is higher so the value of the rotational constant, B, is
smaller. A smaller value of B implies that the lines in the rotational spectrum are closer
together. If the resolution is not good then this may result in a contour/envelope instead
of equally spaced resolved lines.
 Two bond lengths, and , need to be evaluated from the rotational spectrum.
However, only one value of B is obtained from the rotational spectrum.

To overcome the second point the rotational spectrum of two molecules is run – the molecule
ABC and of the isotopically substituted species .

https://media.cheggcdn.com/media%2F827%2F8275db8f-7bb2-485e-87c4-
7cb2da9a903b%2Fimage

Let the atomic masses be mA, mB and mC and let the internuclear distance between atom A and
atom B be and that between atom B and atom C be . Let the centre of gravity (CG) be at
point C. Let the distance between atom A and CG be , that between atom B and the CG be
and that between atom C and the CG be . (According to the above figure, = S).

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Taking moments about CG:

+ =

Also, = + and = +

Therefore = − and

( + )+ = ( − )

( + + ) = −

= − where = ( + + )

=( − )/

Moment of inertia:

Hence: = + +

= ( + ) + + ( − )

= { +2 + }+ + { − 2 + }

= ( + + ) +2 ( − )+ +

= +2 ( − )+ +

Substituting for :

= {( − )⁄ } + 2 {( − )⁄ } ( − )+
+

= {( − ) / } – 2 {( − ) / }+ +

= + - {( − ) / }

Similarly the moment of inertia for the isotopically substituted species will be:

= + - {( − ) / } where =( + + )

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The values of the rotational constants B and are evaluated from the two rotational spectra
run respectively for the molecules ABC and . From these the values of and can be
calculated. Substituting for and in the above two equations the values of the two bond
lengths and can be evaluated.

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Vibrational or Infrared (IR) Spectroscopy

Infrared spectroscopy (IR spectroscopy or vibrational spectroscopy) is the measurement of
the interaction of infrared radiation with matter/sample by absorption or emission. It is used to
study and identify chemical substances or functional groups in solid, liquid, or gaseous forms.
The method or technique of infrared spectroscopy is performed using an instrument called
an infrared spectrometer (or spectrophotometer) which produces an infrared spectrum. An
IR spectrum can be visualized in a graph of infrared light absorbance (or transmittance) on the
vertical axis vs. frequency or wavelength on the horizontal axis. Typical units of frequency
used in IR spectra are . Units of IR wavelength are commonly given in micrometers, μm.

https://en.wikipedia.org/wiki/Infrared_spectroscopy#:~:text=Infrared%20spectroscopy%20(I
R%20spectroscopy%20or,%2C%20liquid%2C%20or%20gaseous%20forms.

The problems considered till now were cases/examples where the potential was either constant
or zero. However, here the potential varies with position. An example of this type of motion is
the vibrations of atoms in molecules and also the vibrational motion of atoms in a crystalline
lattice. When a particle oscillates about its mean position under the action of a force which is
directly proportional to the displacement from its mean position at any instant, it is called a
harmonic oscillator. When the displacement is expressed in terms of a single coordinate, the
oscillator is called a linear harmonic oscillator or a simple harmonic oscillator.

During the vibrational motion, the atoms of a molecule do not remain fixed but vibrate about
a mean position, i.e. there exists elasticity in the bond.

Harmonic oscillator model:

Consider a diatomic molecule AB undergoing vibrational motion within the simple harmonic
oscillator model. Using classical mechanics, if the reduced mass of the molecule is μ, then:

= ; and =− from Hooke s law.

The force constant, k is similar to the ‘spring constant’ used in Hooke’s Law since the
vibrational motion of the atoms A and B about their equilibrium positions results in the bond
behaving like a spring.

Hence: =−

+ =0

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A possible solution to this second order differential equation is of the form:

( )= sin ; where A is a constant.

Since the sine function can have values from -1 to +1, the displacement ( ) can take values
ranging from − to + .

Frequency associated with the vibrational motion, =

The energy associated with this particle, E:

= +

1 1 1
+ = + = +
2 2 2 2 2 2

1
= +
2 2

1
= +
2 2

1
=
2
This is the equation of a parabola. If the energy, E is plotted against displacement then the
minimum displacement, is − and the maximum displacement is + :

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E
n
e
r
g
y

Displacement

Classical laws do not hold for particles of small masses and hence the equation corresponding
to the classical treatment cannot be used for the vibrational motion of a small
particle/atom/molecule.

The expression for the Hamiltonian operator,Ĥ, corresponding to the observable vibrational
energy, is:

Ĥ≡ +

ℏ 1
Ĥ= − +
2 2

Schrodinger’s equation

Ĥ ( )= ( )

ℏ 1
− + ( )= ( )
2 2

On solving the above Schrodinger equation we get the mathematical expressions for and
the wavefunctions, ( ):

= + ℎ in units of Joules (J)

where is the vibrational quantum number and the frequency associated with this vibration
or oscillation (unit : Hz or ) is given by: = .

(In some texts the symbol used for the vibrational frequency is either or ).

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The above expression can also be written as:

= + ħ in units of Joules (J)

In units of wavenumber (i.e ): ( )= = + ̅;

where ̅ = =

The figure below is an example of a diatomic molecule consisting of atoms having mass m
and M:

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https://www.researchgate.net/profile/Christian_Huck/publication/264496330/figure/fig9/AS:
267915899437058@1440887536113/Model-of-the-harmonic-and-anharmonic-
oscillators.png

Note: In the above diagram which shows the equally spaced vibrational energy levels, it is
preferable to label the − axis as Internuclear distance instead of Atomic distance.

From the mathematical expression for the vibrational energy (or also referred to as
( )) it is clear that:

 the energy is quantized – its value depends on the vibrational quantum number, .
 the vibrational energy levels are equally spaced.
 when = 0, = ℎ this is the zero point energy. This implies that the particle is
never at rest; i.e. there is always an uncertainty in position! This is in agreement with
the Heisenberg’s uncertainty principle. In classical mechanics, there is no concept of
zero point energy as the particle can be at rest.
 from the expressions and plots of the wave function, (x), the number of nodes
increase as the value of the vibrational quantum number increases.

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As another example consider a diatomic molecule H1H2 which is undergoing vibrational

motion. Let the atom H1 be fixed at the origin and let the atom H2 be vibrating about its mean
position. As the amplitude of the vibration associated with this second atom changes, there is
a corresponding change in the vibrational energy. The vibrational energy is quantized and can
take only discrete values represented as and .

https://slideplayer.com/slide/10793626/38/images/7/Vibrational+spectra%3A+Harmonic+osc
illator+model.jpg

At the extremes of the vibration, the entire energy is present only as potential energy as the
kinetic energy is zero. Hence the amplitude of the vibration, can be evaluated from:

=( + ) or = ( + )

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To obtain the expression for the eigenfunctions, (x), it is easier to write the above
Schrodinger equation as:
2 1
+ ( − ) ( )=0
ћ 2

Defining a new variable, = √ , where = and ω(angular frequency) = 2 =

ћ

the solution to the Schrodinger’s equation for are given by the Hermite polynomials, .
In these expressions, the subscript represents the vibrational quantum number.

The general expression for is of the form :

√
= exp − .
!√

The expressions for first few Hermite polynomials are:

=1

=2

=4 −2

The expression for the wave functions, ( ) in terms of the variable α (expressed as):

= = = =
ћ ℏ

are:

( )= (− /2)

/
4
( )= (− /2)

4
( )= (2 − 1) (− /2)

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Plots of the expression of the wave functions ( ) are:

https://openstax.org/resources/da589c2ca5119faabbadedab0abc12cdb56f0166

Note:

 The = 0 point marked on the − which represents the internuclear distance in

the above diagram is the same as , i.e. the internuclear bond distance. This implies
that for the diatomic molecule it is considered that one atom of the diatomic molecule
AB is fixed at the origin = 0.
 Also the vibrational quantum number marked above with the letter is the same as the
vibrational quantum number .
 The units on the − axis are units of Energy [units of ℎ or ℎ or ℎ where or
or all represent the same vibrational frequency ]

The selection rule for IR spectroscopy within the harmonic oscillator model is ∆ = ±1. Since
the vibrational levels are equally spaced and transitions must follow the above selection rule,
only one transition will be observed immaterial of the value of and ( + 1). The frequency
corresponding to this transition is called the fundamental absorption frequency.

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Anharmonic oscillator:

P M Morse suggested an empirical relation for the potential. According to this relation, the
potential is a function of the distance, denoted by ( ) and represented as:

( )= [1 − exp − ]

where is the depth of the potential and is known as the spectroscopic dissociation energy
and a is a constant for the molecule whose value depends on the force constant and :

⁄
1 2
= =
2 2

[Units - : ; ∶ = ; : ].

The above expression for ( ) is now used in the Hamiltonian and a new Schrodinger equation
is set-up and solved. The solution to this new Schrodinger equation gives the vibrational energy
within the anharmonic oscillator. In units of wavenumber ( ) the vibrational energy
or or ( )is:

= + − +

In this expression, is the vibrational quantum number, is the equilibrium oscillation

frequency and is the anharmonicity constant. It is a small positive number whose expression
is:

ℎ 1
=
4 2

Since the value of is a small positive number ( has no units), the vibrational levels are no
more equally spaced but are getting closer together as the values of the vibrational quantum
number, , increase. The above expression for the vibrational energy can also be written as:

= 1− ( + ) +

In units of J, the vibrational energy, = + − + ℎ

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https://www.researchgate.net/profile/Christian_Huck/publication/264496330/figure/fig9/AS:
267915899437058@1440887536113/Model-of-the-harmonic-and-anharmonic-
oscillators.png

Note: In the above diagram which shows the vibrational energy levels getting closer together
as the vibrational quantum number increases in accordance with the anharmonic oscillator, it
is preferable to label the − axis as Internuclear distance instead of Atomic distance.

https://upload.wikimedia.org/wikipedia/commons/b/bb/Anharmonic_oscillator.gif

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Comparing the expression for the vibrational energy within harmonic oscillator model with
that obtained when anharmonic oscillations are considered:

= 1− +

Hence the anharmonic oscillator behaves similar to a harmonic oscillator except that in the
anharmonic oscillator, the vibrational frequency rapidly decreases with an increase in the
vibrational quantum number, .

https://lh4.googleusercontent.com/X2QjvJ-E-
sfD1oloDxc5dCA0tD51YirsjYxr_S9n4g2Vgi8rW44b3W1h2QQYElXrNdwBM9E1gREMR
R75Z2YQnXX3Vn-CiUA1KYaOJJS22CdiBl7nmL1W2CCBEg0oiJo=s412

The zero point energy i.e. the vibrational energy corresponding to = 0 within the
anharmonic oscillator is:

= 1− = − .

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The selection rule for the anharmonic oscillator is ∆ = ±1, ±2, ±3 … … The transition
corresponding to ∆ = ±1, is called the fundamental absorption. The transitions
corresponding to ∆ = ±2, ±3 … … are called harmonics or overtones.

The transition probability and hence the intensity of the corresponding spectral lines in the IR
spectrum falls off very rapidly for higher order transitions and hence only transitions till
∆ = ±3 are observed.

Energy

https://www.researchgate.net/profile/A_Obermeier/publication/257144577/figure/fig13/AS:6
69531726942212@1536640211262/Morse-potential-and-vibrational-energy-levels-with-
dissociation-potential-D-e-and.ppm

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In general the spectral lines observed in the IR spectra when the anharmonic oscillator is
considered are:

Lower vibrational Higher vibrational ∆ ∆ / Name of the spectral

quantum number, quantum number, line/transition

0 1 +1 (1 − 2 ) Fundamental
absorption

0 2 +2 2 (1 − 3 ) First overtone/

second harmonic

0 3 +3 3 (1 − 4 ) Second overtone/

third harmonic

0 {1 − ( +1) } harmonic

( + 1) +1 {1 − 2( + 1) }

Since the anharmonicity constant, , is a small positive number, it is evident that the higher
order spectral lines appear at values close to multiples of the fundamental absorption. Hence
they are labelled as harmonics or overtones.

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https://www.researchgate.net/profile/Mulualem_Tigabu/publication/30072372/figure/fig3/AS
:669458322444298@1536622710194/The-energy-of-a-diatomic-molecule-undergoing-
harmonic-oscillation-dashed-line-and.png

The intensity of the spectral lines is governed by the population of the vibrational level.

Let the = 0 level have a population No and let the = 1 level have a population . The
relative population of the vibrational levels follows Boltzmann distribution:
∆ ∆
= exp = .

Usually the spacing between successive vibrational levels is ≅ 10 . If the sample is at

room temperature i.e. 300K, then:

.
= = {−4.8} ≅ 0.01.
.

This implies that the population of the = 1 level is about 1% the population of the = 0
level. Since at room temperature, 99% of the population is in the vibrational ground state, i.e.
the = 0 level, vibrational transitions originating in the higher vibrational states can be
ignored.
If the sample is heated to a temperature of 600K, the ratio of ≅ 0.1.
This implies that the = 1 state has about 10% population and transitions originating in this
state may show as spectral lines in the IR spectrum. Since this line is seen only because of the
higher temperature of the sample, it is called a hotband.

Lower vibrational Higher vibrational ∆ ∆ / Name of the

quantum number, quantum number, spectral
line/transition

1 2 +1 (1 − 4 ) Hotband

Consider the equation for the v’ harmonic:

∆ = ′ {1 − ( ′ +1) }

∆
Or ′
= {1 − ( ′ +1) }
∆
A plot of versus ( + 1) will be a straight line; the intercept will be equal to the value of
and the slope will be equal to .

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In the anharmonic oscillator, vibrational levels are not equally spaced. The levels get closer
and closer together as the value of the vibrational quantum number increases. Hence for high
values of the vibrational quantum number the spacing between two successive vibrational
levels will tend to zero – there are no quantized energy levels now in accordance with the
Correspondence Principle.
Hence:
∆ = {1 − 2( + 1) } → 0.

Or {1 − 2( + 1) } ≅ 0.

If this high value of the vibrational quantum number is called , i.e. the highest possible value of
the vibrational quantum number, then:
{1 − 2( + 1) } = 0

Since ≠ 0; {1 − 2( + 1) }=0

Or 2( + 1) = 1 ; i.e. ( + 1) = or ( + 1) = or = −1

If ≈ 0.01, then = 49.

This implies that the highest possible value of the vibrational quantum number is 49, after this
dissociation occurs and the energy is no more quantized!
Substituting the value of in the expression for , subtracting the zero point energy and converting
the units into will give an estimate of the dissociation energy associated with the sample.

This value of the dissociation energy may sometimes not match with the thermal dissociation energy.
The reason for this is that the mathematical expression for being used here is actually a truncated
series where the higher order terms associated with + and + have been neglected.

A more “correct” expression for the vibrational energy is:

1 3 1 4
= + − + + + + + cm-1
2 2

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https://encrypted-tbn0.gstatic.com/images?q=tbn%3AANd9GcQe5kDJKbZ-
Mu3LhgBAqCBlackw0Wpc0MAr3w&usqp=CAU

https://upload.wikimedia.org/wikipedia/commons/thumb/7/7a/Morse-potential.png/400px-Morse-
potential.png

Force constant of a bond is indicative of the strength of the bond. Calculations for the force
constant, k are most often done following the harmonic oscillator model,
=4
The units for force constant are .
__________________________________________________________________________________

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Problem:
1. The following spectral lines are observed in the IR spectrum of HCl molecule:

Spectral line Wavenumber/

Fundamental absorption 2886

First overtone 5668

Second overtone 8347

Calculate , e and k.

2. The following data has been taken from the IR spectrum of HCl molecule:

Vibrational quantum number ∆

/
( + 1)
0 1 2 2886.0

0 2 3 2834.0

0 3 4 2782.3

Plot a graph and evaluate and e.

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3. Given below is a figure for the HI molecule undergoing vibrational motion within both
the harmonic oscillator model and anharmonic oscillator. Explain briefly the
differences and calculate the fundamental vibrational frequency under the harmonic
oscillator model.

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Vibrations in polyatomic molecules:

Polyatomic molecules undergo complex vibrations that are called normal modes of vibration.
These normal modes of vibration are: asymmetric and symmetric stretches and various types
of bending modes: wagging, twisting, scissoring, and rocking.

For a molecule which has N atoms there are 3N coordinates which need to be known to specify
the molecule unambiguously. Hence there are 3N degrees of freedom. When the molecule
moves in space, the bond angles and bond lengths do not vary however the position of the CG
of the changes. All movement associated with the molecule – translational, vibrational,
rotational can be described in terms of the CG; movement of CG, movement about CG, to and
fro displacement of the CG.

Specifying the CG of the molecule requires 3 coordinates or degrees of freedom. These three
coordinates are called translational degrees of freedom. The remaining (3N-3) degrees of
freedom would then describe the rotational and vibrational motions associated with the
molecule. In general, the rotational motion of a polyatomic molecule can be resolved along
three mutually perpendicular axes. However, if the molecule is linear, one of these axes is along
the internuclear axis and hence the rotational motion will be resolved along only two axes.
Hence, a linear molecule will have two degrees of rotational freedom while a non-linear
molecule will have three degrees of rotational freedom.

This implies that:

 For linear molecules there will be ( − ) vibrational degrees of freedom or

( − ) modes of vibration;
 For non-linear molecules there will be ( − ) vibrational degrees of freedom or
( − ) modes of vibration.

If the molecule is non-cyclic, then an N-atom molecule has ( − 1)) bonds. Each of these
bonds can have a stretching frequency associated with it. Hence for an N atom linear molecule
there will be ( − 1) stretching frequencies/modes of vibration and the remaining (2 − 4)
modes of vibration will be associated with the motions of bending, twisting and scissoring. The
stretching frequencies involve a change in internuclear distance (bond length) and can be
associated both with a symmetric stretch or an asymmetric stretch. The bending modes of
vibrations involve vibrations of the atoms which are such that there is a change in bond angle.

Similarly for a non-linear, non-cyclic − atom molecule, there will ( − 1) bonds which will
have ( − 1) stretching frequencies associated with them. The remaining (2 − 5) modes of
vibration will be associated with the motions of bending, twisting, scissoring etc.

The normal modes of vibration are labelled as where i signifies the different modes of
vibration in the molecule.

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Normal modes of vibrations are classified as either:

 Parallel modes – where the change in dipole moment due to the vibrational motion is
in a direction parallel to the highest order of symmetry axis.
 Perpendicular modes - where the change in dipole moment due to the vibrational motion
is in a direction perpendicular to the highest order of symmetry axis.

Consider the triatomic bent molecule H2O. This molecule has axis of symmetry. To classify
the vibrational modes, the change in dipole moment due to the vibration with respect to this
axis is considered.The presence of the permanent dipole moment ensures that the sample is
IR active. For this molecule, = 3, hence the number of vibrational modes are 3, i.e. = 3.
There are two bonds, this implies that there are 2 stretching modes of vibration – a symmetric
mode and an asymmetric mode. Along with this there is a bending mode of vibration. These
modes are represented as symmetric stretch, asymmetric stretch and bending mode:

https://sites.cns.utexas.edu/sites/default/files/styles/os_files_xlarge/public/jones_ch431/files/s
lide1_0.jpg?m=1484252010&itok=6fnbo5cD

For water molecule, the values corresponding to the three vibrational modes are:

Value of i Type of vibration Wavenumber/ IR active

1 Symmetric stretch – 3651.7 √

parallel mode

2 Bending – parallel mode 1595.0 √

3 Asymmetric stretch – 3755.8 √

perpendicular mode

The subscript i is given values as follows: first the symmetric modes are numbered and then
asymmetric modes are numbered. Within a particular type of vibrations, the number given to i
is in decreasing order of magnitude of the energy/frequency/wavenumber.

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Consider the triatomic linear molecule CO2. This molecule has and axes of symmetry.
However, to classify the vibrational modes, the change in dipole moment due to the vibration
with respect to the axis is considered. For this molecule, = 3, hence the number of
vibrational modes are 4. There are two bonds this implies that there are 2 stretching modes of
vibration – a symmetric mode and an asymmetric mode. Since this molecule does not have a
permanent dipole moment, only those vibrations which have an induced dipole moment due to
the periodic displacement of the atoms will be IR active. Hence, the symmetric mode of
vibration is IR inactive. This frequency is obtained from Raman spectroscopy. Along with the
two stretches, there are two bending modes of vibration. However, these two bending modes
of vibration (one when the atoms move in the plane of paper and the other where the atoms
move perpendicular to the plane of the paper) are degenerate. Hence only 3 vibrational
frequencies are observed. These modes are represented as:

https://lh3.googleusercontent.com/proxy/_wwnxhsV8Or3_jeLwdV3UyTxCqzYZ-
NKlJtQtAgR9LwZfVutFSlIJLb0obIW9O_E2E23m29UUKWUre53FAEMICVoPv1FMTkE
T6KHZZhX2lMSmkfQxypLiDGmC_M9ooVpcl0Zu8p0mxIKFZLv5mdBwm0-
fnrM6zzr41kgfPD5qarT0XzEABR_4N-48YjJ

Value of i Type of vibration Wavenumber/ IR active

1 Symmetric stretch – 1330 X

parallel mode

2 Bending – 667.3 √

perpendicular mode

3 Asymmetric stretch – 2349.3 √

parallel mode

Usually the bending mode of vibration is associated with the least energy / frequency /
wavenumber as this distortion requires the least energy.

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Overtones and Combination frequencies:

Within the anharmonic oscillator there is a possibility of identifying overtones in the spectra.
These overtones occur at wavenumbers close to 2 , 3 … … where corresponds to the
fundamental absorption associated with a particular type of vibrational mode – stretching or
bending.

It has been seen that some spectra are more complex due to the appearance of lines/bands
which appear at wavenumbers corresponding to:

 Difference bands at wavenumbers which are the difference of two fundamental

wavenumbers or the overtones, e.g. at ( − ), (2 − ), (3 − ) … …
 Combination bands at wavenumbers which are the sum of two fundamental
wavenumbers or the overtones, e.g. at ( + ), (2 + ), (3 + ) … …

These usually have low intensity.

An accidental degeneracy can occur between two different fundamental vibrational

frequencies or between one fundamental vibrational frequency and an overtone. If this
accidental degeneracy occurs, then the two bands close together can interact with each other
resulting in an increase in intensity of one and a decrease in intensity of the other. The
accidental degeneracy between a fundamental absorption and an overtone is known as Fermi
resonance. Fermi resonance is usually observed in carbonyl compounds.

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Group vibrations/frequencies:

For polyatomic molecules, normal modes of vibration can be divided into two classes:

Skeletal vibrations – these are due to the vibrations of the ‘skeletal’ structure and arise
from strong coupling between stretching or bending motions of atoms in straight chains,
branched chains or in a ring. All the atoms involved undergo approximately the same
displacement. The frequencies usually fall in the range 1400 – 1700 cm-1.
For example: ‒C‒O‒C‒; ‒C‒C‒C‒


Characteristic functional group vibrations – these involve the vibration of only a
small portion of the molecule (e.g. a functional group) the remaining molecule staying
practically ‘stationary’ during the vibration. These functional group vibrational
frequencies are usually independent of the structure of the molecule.

https://lh3.googleusercontent.com/proxy/NImUvW8JZxzCj8mfrnKzcm8ItJvrH3Pzzc
4VAWdvwpB0-T-sdo-
OxiTiL1FIteObLG2F7yrSS2uGWF8UknEahSAZL9XqMBYjKhsAXSvskWvnOn3C
msYi1Ea5ZdbZadiLIMIdXd-29GNR3eI2OH3EWGm4yMYgyut-
kMumi_kIn7reAMJvJ2s9z8fNfYrz

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Vibrational Rotational Spectroscopy

In molecular spectroscopy, using the Born Oppenheimer approximation implies
considering the molecular energy as a sum of independent terms, e.g:

+ + +
These terms are of different orders of magnitude and the nuclear spin energy is so small that it
is often omitted.

The spacing between rotational levels is approximately≈ 10 , while the spacing between
vibrational level is approximately≈ 10 . For a molecule which is simultaneously rotating
and vibrating, since the rotational and vibrational energies are so different in magnitude it may
be assumed that the two motions are independent of each other. In terms of time period, the
period of vibration is ≈ 10 , while that of rotation is ≈ 10 s. This implies that while the
molecule is undergoing rotational motion the molecule vibrates so rapidly that the molecule is
‘seen’ as having a ‘fixed’ internuclear distance even though it is actually vibrating. Since the
two motions are independent of each other, the molecule can be considered to be
simultaneously a rigid rotator but still vibrating!

The total energy associated with this molecule is:

=( + ) or =( + )

If the vibrational energy is represented as ( ), where is the vibrational quantum number

and the rotational energy is represented as F(J) where J is the rotational quantum number, then:
, ={ ( )+ ( )}

Substituting for the vibrational energy and the rotational energy:

, = + − + + { ( + 1)} .

This implies that the molecule is being considered ‘rigid’ but vibrating! The inclusion of the
centrifugal distortion coefficient D (which accounts for non-rigid rotational motion) does not
alter the value of , much. Since the value of B is independent of vibrational motion, the
rotational levels will be equally spaced within the vibrational levels.

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Diatomic molecules:
For a diatomic molecule, AB, undergoing vibrational and rotational motion, the selection rules
are: ∆ = ±1, ±2 … .. and ∆ = ±1. Since the overtones have relatively low intensity, only
the transition " = 0 → ′ = 1 can be considered.
Let the value of the rotational quantum number be in the " = 0 vibrational state and in
the ′ = 1 state. The change in energy during a transition, ∆ , is:

∆ , = , − ", "

"
∆ , = − + ( + 1) - − + ( " + 1)

= −2 + {( − ")( J' + J" +1)}

= (1−2 )+ {( − ")( J' + J" +1)}

The lines corresponding to the selection rule ∆ = +1 are called the R-branch, while those
corresponding to selection rule ∆ = −1 are called the P-branch.

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(Figure from Molecular Structure and Spectroscopy by G Aruldhas)

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For the R-branch, ∆ = +1, i.e. = ( " + 1) or ( − ") = 1 Substituting in the equation
for ∆ , :
∆ , = ( 1 − 2 ) + 2 ( " + 1) where " = 0,1,2 … ..

For the P-branch, ∆ = −1, i.e. " = ( ′ + 1) or ( − ") = − 1 Substituting in the equation
for ∆ , :
∆ , = ( 1 − 2 ) − 2 ( ′ + 1) where ′ = 0,1,2 … ..

Combining the above two equations for ∆ , :

∆ , = (1−2 )+ 2 ( + 1)

where = 0,1,2 … .. and = −1 for the P-branch and = +1 for the R-branch.

The line corresponding to ( 1 − 2 ) which is a ‘missing’ line is called the band

origin or band centre. As ≠ 0, the missing line actually implies that the transition is
forbidden. The spacing between two successive lines in any of the two branches is 2Bcm-1.
The spacing between the two branches (P-branch and R-branch) is 4Bcm-1.

A typical vibrational rotational spectrum for the heteronuclear diatomic molecule 12C16O is:

https://upload.wikimedia.org/wikipedia/en/thumb/4/42/Vib_rot_CO.png/250px-
Vib_rot_CO.png

The gap in the spectrum above is close to 2140 . The lines to the left of the ‘gap’ are
labelled as the P-branch while those to the right are labelled as R-branch. When the
wavenumber/ increases from left to right in the spectrum recorded, then the lines in the
P-branch from the centre moving towards the left are labelled as , , ….while the lines in
the R-branch from the centre moving towards the right are labelled as , , …..
Conventionally the subscript corresponds to the value of the rotational quantum number .

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https://www.spiedigitallibrary.org/ContentImages/ebooks/FG08/Images/page91-1.jpg

Note: In the above diagram, wavenumber/ is increasing from right to left.

_________________________________________________________________________

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Problem: (as mentioned in the Physical Chemistry V Practical)
The vibrational rotational spectrum of 1H35Cl is:

https://lh3.googleusercontent.com/proxy/m0jj0DBeST6mBwaVlJLafOXMSnHRH_h0DInOb
53MKb6v2jKORVcpnAwRjdpfZLI0od6J2tjN2coayhvE92y7IQXfnBy_tQy6AEqJSeuCSTrZ
71ChsYJFvyPR6iB7UQ
Analyse the spectrum, label the spectral lines within a branch and report the values of B, and
the fundamental vibrational frequency.
(Note: The lines are showing as doublet/split due to the presence of the two isotopes 35Cl and
37
Cl – the former is more abundant – in nature its relative abundance is approximately 70%).
S.No Branch Rotational quantum Frequency/Hz Wavenumber/ Line Spacing
number 2B/cm-1

1. 1 0 --------

2. 2 1

3. P 3 2

4. ∆ 4 3
= −1
5. 5 4

6. 0 1 --------

7. 1 2

8. R 2 3

9. ∆ 3 4
= +1
10 4 5

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Calculate the average value of B. Report the values of the:
 Rotational constant, B,
 Internuclear distance, i.e bond length and
 fundamental vibrational frequency.

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Polyatomic molecules:
Rotational motion affects the vibrational spectra of polyatomic molecules.
The selection rules for the allowed transitions in complex molecules depend on the type of
molecule (linear or non-linear) and the type of vibrational mode (parallel or perpendicular).

Linear molecules:
 Parallel mode of vibrations:
∆ = ±1; ∆ = ±1 for the simple harmonic oscillator model;
∆ = ±1; ∆ = ±1, ±2 … for the anharmonic oscillator.
Since the value of the rotational constant, B, is small, the spacing between successive
lines is small. In some cases the value of B is so small that the lines cannot be resolved
and a PR-contour is observed.

P-branch

R-branch

https://d3i71xaburhd42.cloudfront.net/4a3b48532775227b5d3f4ffeaa12233dc118680
b/16-Figure17-1.png

If the spacing between the points of maxima in the P and R branches is ∆ ̅ ,(↔ in the above
figure) then this value can be used to determine the value of the rotational constant, B.
If the vibrational energy is represented as ( ), where is the vibrational quantum number
and the rotational energy is represented as ( ) where is the rotational quantum number, then:

, ={ ( )+ ( )}

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Substituting for the vibrational energy and the rotational energy:

, = + − + + { ( + 1)} cm-1.

The points of maxima in the P-branch and R-branch will correspond to the value of the
rotational quantum number .

For the R-branch, ∆ = +1, i.e at the point of maxima:

∆ , = (1−2 )+ 2 ( + 1)

For the P-branch, ∆ = −1, i.e at the point of maxima:

∆ , = (1−2 )− 2 ( + 1)

If the spacing between the points of maxima in the P and R branch is ∆ ̅ , then:
∆ ̅=4 ( + 1) .

Substituting for :

∆ ̅ = 4B − +1 = 4 + = +2 = +2

However, for a polyatomic molecule B and hence 2B are small. Hence:

(∆ )
∆ ̅ ≅ or =

PR-contours are usually observed only in linear molecules.

 Perpendicular mode of vibrations:
∆ = 0, ±1; ∆ = ±1 for the simple harmonic oscillator model;
∆ = 0, ±1; ∆ = ±1, ±2 … for the anharmonic oscillator.
Since the value of the rotational constant, B, is small, the spacing between successive
lines is small. In some cases the value of B is so small that the lines cannot be resolved
and a PQR-contour is observed.
Here a vibrational change can occur without a simultaneous change in the rotational
quantum number; i.e. ∆ = 0 is an allowed transition. The Q-band transitions will all
occur at the same value for all values of J and hence the Q-band is intense.
However, if B is small the lines in the P- branch and R-branch will not be resolved and
the PQR contour shown below is observed:

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https://en.wikipedia.org/wiki/File:Vibrationrotationenergy.svg

Q-band

P-branch R-branch

Wavenumber/cm-1
https://ars.els-cdn.com/content/image/3-s2.0-B0123693977002740-gr7.jpg

As mentioned earlier, if the spacing between the points of maxima in the P and R branches is
∆ ̅ ,(↔ in the above figure) then this value can be used to determine the value of the rotational
constant, B.

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If the lines within the P-branch and R-branch can be resolved, the spectrum would appear as
below, where the spacing between successive lines in the same branch is 2 :

https://encrypted-
tbn0.gstatic.com/images?q=tbn%3AANd9GcRamwWWggLpHGzM7gZsQZicjtq9FU
bEoWXcRw&usqp=CAU

https://media.springernature.com/lw785/springer-
static/image/chp%3A10.1007%2F978-3-642-54313-
5_4/MediaObjects/216251_1_En_4_Fig9_HTML.gif

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RAMAN SPECTROSCOPY

Raman spectroscopy is an analytical technique where scattered light is used to measure the
vibrational energy modes of a sample. It is named after the Indian physicist C. V. Raman
who, together with his research partner K. S. Krishnan, was the first to observe Raman
scattering in 1928. Raman spectroscopy can provide both chemical and structural
information, as well as the identification of substances through their characteristic Raman
‘fingerprint’. Raman spectroscopy extracts this information through the detection of Raman
scattering from the sample.

As mentioned, Raman spectroscopy is a molecular spectroscopic technique that utilizes the

interaction of light with matter to gain insight into the characteristics of the material/sample,
very much like IR spectroscopy. The information provided by Raman spectroscopy results from
a light scattering process, whereas IR spectroscopy relies on absorption of light. Scattering
implies a change in direction of the incident photon. There may not be a change in the energy.
On the other hand, absorption of a photon always implies a change in energy. Raman
spectroscopy yields information about intra- and inter-molecular vibrations and can provide
additional understanding about a reaction or the structure of a molecule. Both Raman and IR
spectroscopy provide a spectrum characteristic of the specific vibrations of a molecule
("molecular fingerprint') and are valuable for identifying a substance. However, Raman
spectroscopy can give additional information about lower frequency modes, and vibrations that
give insight into crystal lattice and molecular backbone structure.

When light interacts with molecules in a gas, liquid, or solid, the vast majority of the photons
are dispersed or scattered at the same energy as the incident photons. This is described as elastic
scattering, or Rayleigh scattering. Here the frequency of the incident radiation is not altered
by the interaction but usually the phase of the electromagnetic radiation is changed. An
example of scattering is the deflection of the sun’s rays when they pass through the clouds. In
the lower portion of the atmosphere, scattering may be caused by the presence of pollen, dust,
smoke, water droplets that are present. Scattering usually occurs when the particles causing the
scatter are larger than the wavelength of the incident radiation. Mathematical derivations
associated with Rayleigh scattering have shown that the higher frequency colours such as blue
and violet are scattered to a greater extent than the low frequency colours like red and orange.
Mathematically the intensity of the scattered light is proportional to the fourth power of the
frequency of the incident radiation. The sky appears blue on a clear cloudless day as the
molecules present in the atmosphere scatter blue light from the sun more than they scatter red
light. This scattered blue light is incident on the eyes.

A small number of these photons, approximately 1 photon in 10 million will scatter at a

different frequency than the incident photon. This process is called inelastic scattering and was
first predicted by Adolf Smekal in 1923. The phenomena was first observed by Sir C V Raman
and called the Raman Effect. In 1930, the Nobel Prize in Physics was awarded to
Sir Chandrasekhara Venkata Raman , "for his work on the scattering of light and for the

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discovery of the effect named after him". Since then, Raman spectroscopy has been utilized for
a vast array of applications from medical diagnostics to material science and reaction analysis.

When a beam of light passes through a ‘transparent’ substance a small amount of the radiation
energy is scattered. If the incident radiation is monochromatic, the scattered energy/radiation
will consist almost entirely of radiation at the incident frequency. As mentioned above, this is
called Rayleigh scattering. If in addition, certain discrete frequencies above and below the
incident radiation are observed then this is referred to as Raman scattering.

The Raman Scattering Process, as described by quantum mechanics, is when photons interact
with a molecule, the molecule may be advanced to a higher energy state (sometimes referred
to as a virtual state). From this higher energy state, there may be a few different outcomes. One
such outcome would be that the molecule relaxes to a vibrational energy level that is different
than that of its beginning state producing a photon of different energy. The difference between
the energy of the incident photon and the energy of the scattered photon is the called the Raman
shift.

If there is no exchange of energy between the incident radiation at frequency and the sample,
i.e. the collision is perfectly elastic then only Rayleigh scattering occurs. However, if energy
is exchanged between the incident radiation and the sample then the collision is inelastic. The
molecule can gain or lose energy in accordance with the laws of quantum mechanics. If the
energy change is ∆E then this must represent a change in either the vibrational or rotational
energy associated with the sample/molecule. If the sample/molecule gains energy, the incident
photon, after the interaction, will be observed at (ℎ − ∆ ); while if the molecule loses energy
then the incident photon, after the interaction, will be observed at (ℎ + ∆ ).

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https://upload.wikimedia.org/wikipedia/commons/thumb/4/41/Raman_energy_levels.svg/450
px-Raman_energy_levels.svg.png

(Note: The virtual state is not a stationary state of the system. It is not a solution of a time-
independent Schrödinger equation and so does not correspond to a well-defined value of the
energy. The virtual states arise from perturbation theory, and should best be viewed as just that
- "virtual/imaginary". The concept can be used to predict and describe experimental results in
many areas including Raman spectroscopy, non-linear optics, some aspects
of photochemistry and in some nuclear processes too.)

When the change in energy of the scattered photon is less than the incident photon, the
scattering is called Stokes scatter or Stokes radiation. Some molecules may begin in a
vibrational excited state and when they are advanced to the higher energy virtual state, they
may relax to a final energy state that is lower than that of the initial excited state. This scattering
is called anti-Stokes.

Since Raman Effect is an inherently weak effect, the optical components of a Raman
Spectrometer must be well matched and optimized. Usually only 1 in 10 molecules undergoes
inelastic scattering. The scattered photons due to the inelastic collisions have frequency shifts
in the range 10 − 4000 . These shifts are characteristic of the changes in either the
vibrational or rotational energies or both vibrational and rotational energy in the
sample/molecule.

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When light is scattered by molecule, the oscillating electromagnetic field of a photon induces
a polarisation of the molecular electron cloud which leaves the molecule in a higher energy
state with the energy of the photon transferred to the molecule. This can be considered as the
formation of a very short-lived complex between the photon and molecule which is
commonly called the virtual state of the molecule. The virtual state is not stable and the
photon is re-emitted almost immediately, as scattered light.

In the vast majority of scattering events, the energy of the molecule is unchanged after its
interaction with the photon; and the energy, and therefore the wavelength, of the scattered
photon is equal to that of the incident photon. This is called elastic (energy of scattering
particle is conserved) or Rayleigh scattering and is the dominant process.

In a much rarer event (approximately 1 in 10 million photons) Raman scattering occurs,

which is an inelastic scattering process with a transfer of energy between the molecule and
scattered photon. If the molecule gains energy from the photon during the scattering (excited
to a higher vibrational level) then the scattered photon loses energy and its wavelength
increases which is called Stokes Raman scattering (after G. G. Stokes). Inversely, if the
molecule loses energy by relaxing to a lower vibrational level the scattered photon gains the
corresponding energy and its wavelength decreases; which is called Anti-Stokes Raman
scattering. Quantum mechanically Stokes and Anti-Stokes are equally likely processes.
However, with an ensemble of molecules, the majority of molecules will be in the ground
vibrational level (Boltzmann distribution) and Stokes scatter is the statistically more probable

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process. As a result, the Stokes Raman scatter is always more intense than the anti-Stokes
and for this reason, it is nearly always the Stokes Raman scatter that is measured in Raman
spectroscopy.

https://www.edinst.com/blog/what-is-raman-spectroscopy/

Unlike IR Spectroscopy that requires either a permanent dipole moment or a change in dipole
moment, Raman spectroscopy requires changes in the polarizability of the molecular bonds.
Interaction of light with a molecule can induce a deformation of its electron cloud. This
deformation is known as a change in polarizability. When a molecule is placed in an electric
field, the electron charge cloud gets distorted. The positively charged nuclei are attracted
towards the negative pole of the electric field and the negatively charged electron cloud is
attracted to the positive pole. This separation of charge centres causes the molecule to now
have an induced dipole moment, . The magnitude of the induced dipole moment is
proportional to the magnitude of the electric field, E. The polarizability, ⍺, is the constant of
proportionality. Therefore, = .

https://i.ytimg.com/vi/7Koa4Lei9iU/maxresdefault.jpg

Molecular bonds have specific energy transitions in which a change of polarizability occurs,
giving rise to Raman active modes. As an example, molecules that contain bonds between
homonuclear atoms such as carbon-carbon, sulfur-sulfur, and nitrogen-nitrogen undergo a
change in polarizability when photons interact with them. These are examples of bonds that
give rise to Raman active spectral bands, but would not be seen in IR spectroscopy.

https://www.mt.com/in/en/home/applications/L1_AutoChem_Applications/Raman-
Spectroscopy.html#:~:text=The%20Raman%20Spectroscopy%20Principle,elastic%20scatteri
ng%2C%20or%20Rayleigh%20scattering.

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When a molecule/sample is placed in the path of the incident electromagnetic radiation at

frequency , then the electrical field experienced by the molecule is:

= sin 2

The induced dipole moment is directly proportional to the polarizability of the molecule,
⍺. Hence: = = ( sin 2 ).

This induced dipole moment can oscillate at its own frequency. If the molecule is undergoing
vibrational motion or rotational motion at a frequency or then the oscillating dipole
will have superimposed on it the corresponding vibrational or rotational motion. The
polarizability will now be a sum of two terms – one due to the equilibrium polarizability ⍺ ,
and the other due to the rate of change of the polarizability because of the vibrational or
rotational motion. If represents the rate of change of polarizability due to the vibrational (or
rotational motion), then: = + sin 2 .

Hence, = = + sin 2 ( sin 2 )

= ( sin 2 )+ (sin 2 )(sin 2 )

= ( sin 2 )+ {cos (2 ( − ) − cos (2 ( + ) }

[ = {cos( − ) − cos( + )}]

This equation implies that the oscillating dipole has frequency components at ( ± ) as
well as at the incident frequency . These two frequency components at ( ± ) explain the
Raman shift and also the observance of both Stokes and anti-Stokes lines.

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Polarizability Ellipsoid:

Consider the diatomic molecule H2 which is inactive in IR spectroscopy as it does not have a
permanent dipole moment. If this molecule is placed in an external electric field then the
direction of the internuclear axis with respect to the direction of the external electric field will
govern the distortion of the electron charge cloud and the subsequent magnitude of the induced
dipole moment, . This implies that the molecule is anisotropic as far as the polarizability
is considered.

Polarizability is a tensor quantity. The physical meaning of the polarizability tensor is that an
electric field in one direction induces distortions not only along the direction of the electric
field but also along the other directions. Considering the three directions of the electric field
( , , ), there will be nine components of the polarizability which can be labelled as
, , , , , , , , . Polarizability of symmetric molecules is usually asymmetric.
The polarizability of a molecule is represented by an ellipsoid.

When the electric field is parallel to the internuclear axis, the distortion of the charge cloud is
much more than the distortion which occurs when the electric field is perpendicular to the
internuclear axis. Measurements have shown that the magnitude of the induced dipole moment
when the electric field is parallel to the internuclear axis, is approximately twice the induced
dipole moment when the electric field is perpendicular to the internculear axis. Since the
magnitude of the electric field, E, remains the same in both the above cases the difference in
the magnitude of the induced dipole moment, , is due to the difference in the magnitude
of the polarizability, ⍺.

The polarizability of a molecule in various directions is represented by a three dimensional

surface called the polarizability ellipsoid. The outer surface of this polarizability ellipsoid is
such that for a point i on the surface, the distance of the surface from the electrical centre of
the molecule is proportional to where ⍺ represents the polarizability along the line joining
point i on the surface to the electrical centre of the molecule. Thus if the polarizability is high
the distance from the electrical centre is small.

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https://www.cdeep.iitb.ac.in/webpage_data/nptel/Core%20Science/Engineering%20Chemistr
y%201/Slide/lect15/Equations%20&%20images/15_8_clip_image002.jpg

The above diagram shows the polarizability ellipsoid for H2 molecule when:
(a) the electric field is perpendicular to the internuclear axis and
(b) the electric field is parallel to the internuclear axis.

In order to be Raman active, a particular mode of rotation, vibration or rotational

vibration must cause a change in either the magnitude or direction of the polarizability
ellipsoid.

In the expression for the induced dipole moment, , it is clear that if = 0, there will be no
change in the equilibrium polarizability and the induced dipole moment will oscillate only at
the frequency corresponding to the incident radiation. This amounts only to Rayleigh scattering
and no Raman shift. Hence if = for a particular mode of rotation, vibration or
rotational vibration then the mode will be Raman inactive.

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Pure rotational Raman spectroscopy:

For linear molecules which are undergoing rotational motion within the rigid rotator
approximation, the rotational energy is: = ( + 1) .

The ‘formal’ selection rule based on a mathematical derivation is ∆ = 0, ±2.

However, ∆ = 0, implies Rayleigh scattering and can be ignored.

The change in rotational energy is:

∆ = ( + 1) − ( + 1)

The change in energy corresponding to the transitions → when ∆ = +2 implies that

the rotational quantum number increases by 2, i.e.

− = 2 or = +2

Hence:

∆ = ( + 2)( + 3) − ( + 1) = (4 + 6); where = 0, 1, 2 …

The change in energy corresponding to the transitions → ′ when ∆ = −2 similarly

implies that the rotational quantum number reduces by 2, i.e.

− = - 2 or = ( + 2)

Hence: ∆ = ( + 1) − ( + 2)( + 3 ) = − (4 + 6); where = 0, 1, 2 …

Hence combining the above equations, the Raman lines appear at:

± { (4 + 6)} where = 0, 1, 2, 3 … ..

If the molecule gains energy when it interacts with the incident radiation at , the transmitted
radiation will give rise to Stokes lines: = – { (4 + 6)}.

If the molecule loses energy when it interacts with the incident radiation at , the transmitted
radiation will give rise to Anti - Stokes lines: = + { (4 + 6)}.

The stick-line spectrum is shown in the figure below:

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https://ars.els-cdn.com/content/image/3-s2.0-B9780323461405000054-f05-03-
9780323461405.jpg

https://encrypted-tbn0.gstatic.com/images?q=tbn%3AANd9GcQn-
iz5mpBFK7Q0vLin63uaaBdFdXkLmTh31w&usqp=CAU

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Molecular data obtained for some homonuclear diatomic molecules from Raman rotational
spectroscopy:

Molecule Bond length /

0.07413
0.10976
0.14180

(from Fundamentals of Molecular Spectroscopy by Banwell and McCash)

For molecules like H2, O2 which have a centre of symmetry, the spin of the nucleus affects the
population of the rotational levels. The nuclear spin for oxygen, I, is zero hence every alternate
rotational level has zero population. Due to this every alternate line is missing in the Stokes
and Anti-Stokes branches. The nuclear spin for hydrogen, I, is ½, hence every alternate
rotational level has lower population. Due to this the lines also show an alternation of intensity.
The figure below shows the rotational Raman spectrum for a diatomic homonuclear molecule
with nuclear spin, I ≠ :

https://slideplayer.com/slide/5218520/16/images/19/Alternate+intensities.jpg

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Pure vibrational Raman spectroscopy:

Raman activity of vibrational modes:

When a molecule has no centre of symmetry then usually all vibrational modes are Raman
active. However, when the molecule has considerable symmetry it is not always so.

Water molecule:
The non-linear water molecule has (3 − 6) = 3 modes of vibrational motion. These three
modes are symmetric stretch, asymmetric stretch and bending. All these three modes are both
IR active (permanent dipole moment) and Raman active. The Raman activity is due to the
change in direction/magnitude of the polarizability ellipsoid during the vibrational motion.
 Symmetric stretch: In this mode of vibration either both the O-H bonds are elongated
or both are compressed at the same time. When the O-H bonds in water molecule are
elongated, the electrons are less firmly held by the nuclei so the bond becomes more
polarizable. An increase in the polarizability from the equilibrium polarizability ⍺
implies a decrease in the magnitude of the polarizability ellipsoid. If the vibrational
motion causes a decrease in the bond lengths of the two O-H bonds, the polarizability
decreases and the magnitude of the polarizability ellipsoid increases.
 Bending mode: In this mode of vibration there is a change in bond angle. As compared
to the equilibrium polarizability ellipsoid, the shape of the polarizability ellipsoid
changes the most during this mode of vibration.
 Asymmetric stretch: In this mode of vibration if one of the bonds gets elongated the
other decreases in length or vice versa. Hence, the shape and the size of the
polarizability ellipsoid remains practically the same as that for the equilibrium situation
but the direction of the major axis of the polarizability ellipsoid changes.

The change in the polarizability ellipsoid magnitude and/or direction occurring during the
above three modes of vibration is shown in the figure below. The central column depicts
the polarizability ellipsoid under equilibrium conditions, i.e. ⍺ .

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https://image.slidesharecdn.com/ramanpol-140924032647-phpapp01/95/raman-spectroscopy-
17-638.jpg?cb=1411529885.

Carbon dioxide molecule:

The linear carbon dioxide molecule has (3 − 5) = 4 modes of vibration. These four modes
are symmetric stretch which is IR inactive but Raman active; asymmetric stretch and the two
degenerate bending modes. Due to the induced dipole moment in the asymmetric stretch and
the bending mode, these two modes of vibration are IR active. However these two modes are
Raman inactive. The Raman inactivity and activity of these vibrational modes is confirmed by
analysing the polarizability ellipsoid.
 Symmetric stretch: The symmetric stretch implies an elongation of both the C-O bonds
simultaneously to the same extent or the compression of the two C-O bonds
simultaneously to the same extent. Let the equilibrium polarization be represented as
⍺ . Let these motions be understood in terms of a displacement coordinate ξ.
Let ξ = 0 imply the equilibrium situation and let ξ be positive for elongation and ξ be
negative for compression. A plot of polarizability, α versus ξ would then be such that
the value of the slope ≠ 0, implying that this mode of vibration is Raman

active.

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 Bending mode: This mode of vibration involves the change in bond angle. Either there
is an increase in bond angle or a decrease in bond angle. As above, the changes in the
polarizability, α as compared to the equilibrium polarizability, ⍺ are explained in
terms of the displacement coordinate, ξ. The increase in bond angle corresponds to ξ
being positive and a decrease in bond angle corresponds to ξ being negative. The change
in polarizability due to the change in bond angle is the same whether the bond angle
increases or decreases. Hence a plot of polarizability, α versus ξ would then be such
that the value of the slope = 0, implying that this mode of vibration is Raman

inactive.
 Asymmetric stretch: In this mode of vibration one C-O bond undergoes an elongation
while the other undergoes a simultaneous compression. This vibration causes an
induced dipole moment and hence this mode of vibration is IR active. As above, the
changes in the polarizability, α as compared to the equilibrium polarizability, ⍺ are
explained in terms of the displacement coordinate, ξ. Let the elongation of any one of
the C-O bonds be represented as ξ positive and the compression of this same bond be
represented by ξ negative. The change in polarizability due to the change in bond length
of this C-O bond is the same whether the bond length increases or decreases. Hence a
plot of polarizability, α versus ξ would then be such that the value of the slope
= 0, implying that this mode of vibration is Raman inactive.

The change in the polarizability ellipsoid magnitude and/or direction occurring during the
above three modes of vibration is shown in the figure below. The central column depicts
the polarizability ellipsoid under equilibrium conditions, i.e. αeq

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https://www.google.com/url?sa=i&url=https%3A%2F%2Ffanyv88.com%3A443%2Fhttps%2Fslideplayer.com%2Fslide%2F383
7254%2F&psig=AOvVaw3KbSIa8GzDrKom3gQHf9d0&ust=1634970253970000&source=i
mages&cd=vfe&ved=0CAsQjRxqFwoTCJDoiYex3fMCFQAAAAAdAAAAABAK
Symmetric vibrations have a large value of and give rise to intense lines in the Raman
vibrational spectrum. The term β mentioned earlier which represented the change in
polarizability due to a vibrational/rotational mode is identical to mentioned here.

Rule of mutual exclusion:

If the molecule has a centre of symmetry then Raman active vibrations are IR inactive and vice
versa. The converse of this rule also holds. This implies that on comparison of the IR and
Raman spectra of a particular molecule if there are no common lines then it can be concluded
that the molecule has a centre of symmetry.
As a result of this fundamental difference, it is often said that Raman and Infrared (IR) Spectra
are complementary, meaning that, between the two, the analysis can lead to a fairly complete
picture of the vibrational modes of a molecule.

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For Raman vibrational spectra, the vibrational energy, in accordance with the anharmonic
oscillator is:

= + − + .

The selection rule is ∆ = ±1, ±2, ±3 … …

However, at room temperature the = 0 has 99% of the population so only those vibrations
originating in this vibrational level will be observed. Also since Raman scattered light is of low
intensity, the overtones (∆ = ±2, ±3 … … ) can be overlooked and only the fundamental
absorption (∆ = ±1) needs to be considered.

Hence the lines that will be observed will be:

={ − (1 − 2 )}

={ + (1 − 2 )}

The Stokes lines correspond to ∆ = +1 and the Anti-Stokes lines correspond to ∆ = − 1

̅/

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Physical Chemistry V – reading material only for the students at Miranda House, University of Delhi 2021
Note: ̅ marked in the above figure is the same as in the above equation. Actually ̅
should have been written as since ̅ is the variable on the − axis in this stick-line
spectrum.

https://cnx.org/resources/7f0765bd23e1ccd3c615ea0724e160c6d01a677c/Fig4a.jpg

Data obtained from Raman vibrational spectroscopy for some diatomic homonuclear
molecules:

Molecule Fundamental vibrational frequency /

4160

2331

1555

892

556

(from Atomic and Molecular Spectroscopy by Mool Chand Gupta)

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 [DOCUMENT TITLE]
Physical Chemistry V – reading material only for the students at Miranda House, University of Delhi 2021
Polarization of light and the Raman effect:

If light is passed through a polariser, e.g. a Nicol’s prism, the transmitted light is called
polarized light. This polarized light has all its electrical vectors parallel to a given plane. If this
polarized light is incident on an analyser then it will ‘pass’ through this analyser undiminished
in intensity only if the polarizing axes of both the Nicol’s prism (polarizer) and the analyser
are parallel to each other. When the two axes are perpendicular to each other no light will be
detected after the analyser. This implies that an analyser can determine the plane of
polarization.

Raman scattered light is found to be plane polarized to different extents even if the exciting (or
incident) radiation is completely unpolarised. If completely plane polarized light is passed
through an analyser, the light will be completely extinguished when the axis of polarization of
the analyser (detector) is perpendicular to the plane of polarization. On the other hand, when
its axis is parallel to the plane of polarization it will be transmitted without any decrease in
intensity.

In the case of Raman vibrational spectroscopy, the symmetric modes of vibration can be
differentiated from the others by using polarized light. The depolarization ratio is defined as
the intensity ratio between the perpendicular component and the parallel component of Raman
scattered light.

Early work in this field was carried out by George Placzek, who developed the theoretical
treatment of bond polarizability.
The Raman scattered light is emitted by the stimulation of the electric field of the incident light.
Therefore, the direction of the vibration of the electric field, or polarization direction, of the
scattered light might be expected to be the same as that of the incident light. In reality, however,
some fraction of the Raman scattered light has a polarization direction that is perpendicular to
that of the incident light. This component is called the perpendicular component. Naturally,
the component of the Raman scattered light whose polarization direction is parallel to that of
the incident light is called the parallel component, and the Raman scattered light consists of
the parallel component and the perpendicular component.
The ratio of the peak intensity of the parallel and perpendicular component is known as the
depolarization ratio ρ:

= =

The value of the depolarization ratio of a Raman band depends on the symmetry of the molecule
and the normal vibrational mode. From Placzek’s polarizability calculations, it is known that
the depolarization ratio of a totally symmetric vibrational mode is less than 0.75, and that of
the other modes equals 0.75. A Raman band whose depolarization ratio is less than 0.75 is
called a polarized band, and a band with a depolarization ratio equal to or greater than 0.75 is
called a depolarized band.
https://en.wikipedia.org/wiki/Depolarization_ratio

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 [DOCUMENT TITLE]
Physical Chemistry V – reading material only for the students at Miranda House, University of Delhi 2021
Let the incident light be along the x-axis and let the analyser be along the – plane. If is
the intensity of the scattered light perpendicular to the - plane (parallel to the - plane)
and ∥ is the intensity of the scattered light parallel to the – plane, then the depolarization
ratio is defined as:

= .
∥

If is zero then is also zero. If = ∥, then = 1.

As mentioned above, precise calculations have shown that the value of is such that if its value
is < 3⁄4 (0.75) the vibration in the molecular sample is a symmetric mode of vibration. The
corresponding Raman line is called a polarized Raman line. A value of ≥ 3⁄4 implies that
the vibration in the molecular sample is non-symmetric/asymmetric and the corresponding
Raman line is called a depolarized Raman line. The important rule is that only symmetric
vibrations can give rise to polarized Raman lines. A measurement of the value of for a
particular Raman spectral line helps in its assignment to an appropriate vibrational mode and
in the determination of the molecular structure.

[Note: In some text books the value of ≥ 6⁄7 (0.85) or even ≥ 2⁄3 (0.67) implies that
the vibration in the molecular sample is non-symmetric/asymmetric and the corresponding
Raman line is called a depolarized Raman line.]

For a spherical top molecule in which all three axes are equivalent, symmetric vibrations have
Raman spectral bands which are completely polarized (ρ = 0). An example is the symmetric
stretching or "breathing" mode of methane (CH4) in which all 4 C–H bonds vibrate in phase.
However for the asymmetric mode in which one C–H bond stretches while the other three
contract, the Raman scattered radiation is depolarized.
For molecules of lower symmetry (symmetric tops or asymmetric tops), a vibration with the
full symmetry of the molecule leads to a polarized or partially polarized Raman band (ρ <
0.75), while a less symmetric vibration yields a depolarized band (ρ ≥ 0.75).

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Physical Chemistry V – reading material only for the students at Miranda House, University of Delhi 2021

For certain molecules and samples, ‘normal’ Raman spectroscopic data can be enhanced by
controlling the polarisation of light exciting the sample, and of light scattering from it.
Analysis of Raman spectra gathered using this technique can provide information about the
molecular structure of a sample, including the symmetry of its vibrational modes, as well as
information about highly-ordered samples, such as crystals, polymers, and carbon materials.
The positions of peaks in Raman spectra can be assigned to the molecular vibrations within
the molecule(s) comprising the sample under analysis. While Raman spectroscopy under
standard conditions tells us about the chemical composition of a sample, polarised Raman
spectroscopy can provide further information, such as the symmetry of vibrational modes,
and the orientation of the sample.
Raman scattered light comprises a combination of light with a polarisation parallel to that of
the excitation light, and with a polarisation perpendicular to it. During standard Raman
measurements, both of these components are measured in the same spectrum. In contrast,
during polarised Raman measurements, polarising filters are used to measure the Raman
spectra of each component separately.
https://www.edinst.com/us/polarised-raman-spectroscopy/

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

Vibration – rotational Raman spectroscopy:

If the vibrational energy is represented as ( ), where is the vibrational quantum number

and the rotational energy is represented as ( ) where is the rotational quantum number, then:

, ={ ( )+ ( )}

Substituting for the vibrational energy and the rotational energy:

, = + − + + { ( + 1)} .

The selection rule for the transitions that can occur is: ∆ = ±1 and ∆ = 0, ±2 .

Considering only the Stokes lines/branch, ∆ = +1, i.e.

={ − (1 − 2 )} cm-1.

The Stokes’ lines corresponding to ∆ = 0, will occur at:

={ − (1 − 2 )} cm-1.

The Stokes’ lines corresponding to ∆ = +2, will occur at:

=[ −{ (1 − 2 )+ (4 + 6)}] cm-1.

= − 1−2 − (4 + 6) cm-1.

The Stokes’ lines corresponding to ∆ = −2, will occur at:

=[ −{ (1 − 2 )− (4 + 6)}] .

= − 1−2 + (4 + 6) .

The various lines in the S- branch and O- branch and the Q-branch occur at:

∆ Branch ∆ , /cm-1

0 Q − (1 − 2 )

+2 S − (1 − 2 ) − (4 + 6)

-2 O − (1 − 2 ) + (4 + 6)

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

A typical spectrum would then appear as below:

(Figure from Molecular Structure and Spectroscopy by G Aruldhas)

Note: In the above figure:

 wavenumber, increases from the left to right;

 on the extreme right ≡ ;
 (1 − 2 ) ≡ (1 − 2 )
 on the extreme left, the S-branch is marked as
 the O-branch is marked as

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https://www.google.com/url?sa=i&url=https%3A%2F%2Ffanyv88.com%3A443%2Fhttp%2Feveryscience.com%2FChemistry%
2FPhysical%2FVibrational_Spectroscopy%2Ff.1024.php&psig=AOvVaw04Ye6U2fW_hVc
aPlGuub7I&ust=1604677093231000&source=images&cd=vfe&ved=0CAIQjRxqFwoTCKjf
q5Xe6-wCFQAAAAAdAAAAABAD

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

ELECTRONIC (Ultraviolet / UV and Visible) SPECTROSCOPY

The Born Oppenheimer approximation in the current context is:

= { + + }

={ + + }

In terms of the quantum numbers,

= { + + } ,

where ε, and are the electronic, vibrational and rotational quantum numbers respectively.

The change in energy due to transitions amongst energy levels:

∆ = {∆ + ∆ + ∆ }

∆ = {∆ + ∆ + ∆ }

The approximate orders of magnitude of the energy changes are:

∆ ≈ (103 x ∆ ) and ∆ ≈ (103 x ∆ )

https://chem.libretexts.org/@api/deki/files/125629/CNX_UPhysics_42_02_Trans.jpg?revisio
n=1

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

The vibrational transitions will produce a “coarse” structure within the electronic transitions
and the rotational transitions will produce a “fine” structure within the “coarse” structure due
to the vibrational transitions within the electronic transitions. Pure rotational (microwave)
spectra can only be observed for those molecules which have a permanent dipole moment, pure
vibrational (infrared/IR) spectra can be observed for those molecules which have either a
permanent dipole moment or an induced dipole moment due to a particular type of vibrational
motion. However, electronic spectra can be observed for all molecules since an electronic
transition will necessarily cause a change in the electronic distribution and hence a dipole
moment. Hence all molecules, including homonuclear molecules (H2, N2, O2 etc) which show
no microwave, IR or vibrational-rotational spectra will show an electronic spectrum. From the
electronic spectra, it is possible to evaluate bond vibrational frequencies, or ,
anharmonicity constant, and rotational constant, .

Vibrational coarse structure:

Neglecting the rotational fine structure, the earlier equations can be rewritten as:

= { + } or ={ + } ,

where ε and are the electronic and vibrational quantum numbers respectively.

i.e. ∆ = {∆ + ∆ }

In units of wavenumber/ cm-1:

∆ = {∆ + ∆ }

Substituting for the vibrational energy, :

= + + 1− +

If the electronic quantum numbers are ε΄ and ε΄΄ (higher and lower level respectively) and the
vibrational quantum numbers are and (higher and lower level respectively), then:

∆ = [( − )+ ( − )]

=( − )

+ + 1− + − + 1− + cm-1

In the above equation the first term gives rise to an electronic transition and the second term
will give rise to the vibrational coarse structure within this electronic transition. The energy
level diagram and the corresponding spectrum due to the vibrational coarse structure is as
shown below:

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

(Diagram from Fundamentals of Molecular Spectroscopy by Banwell and McCash)

There is no selection rule for the vibrational coarse structure. Since the = 0 is the most
populated at room temperature the absorption spectrum can be approximated as a series of lines
consisting of transitions originating in the = 0 state.

As shown in the diagram above, the lines in the stick-line spectrum are labelled according to
their ( , ) numbers, i.e. (0,0); (1,0); (2,0) ….. Since the value of the vibrational quantum
number, is steadily increasing, the spectrum is referred to as a - progression. Under low-
resolution, the separate or distinct lines may not be visible and hence this is also known as a
-band. In the mathematical expression above, since χe (anharmonicity constant) is a small
positive number, the vibrational levels for higher values of v΄ are closer together. This implies
that the lines in the − progression are not equally spaced but are in fact getting closer
together. At higher values of , the lines will get bunched together; this is called the
convergence limit.
The intensity of the lines in the - progression is given by the Franck – Condon Principle.

This principle states that since an electronic transition occurs rapidly, a vibrating molecule
does not change its internuclear distance appreciably during the transition.

As discussed (earlier in vibrational (Infrared/IR) spectroscopy), the energy of a diatomic

molecule varies with internuclear distance. Following the Morse potential energy expression
for ( ) and the subsequent plot of vibrational energy as a function of internuclear distance, if

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

one atom of the diatomic molecule is assumed fixed at the origin then the second atom will
oscillate between the extremes of the Morse curve. Classical theory suggests that the oscillating
atom will spend most of its time at the extremes of the curve when the motion of this atom is
reversed.

However, quantum theory agrees with this only at high values of the vibrational quantum
number, . At the vibrational ground state, i.e. = 0, the atom tends to spend most of its time
at the centre of the curve. At vibrational quantum numbers, = 1, = 2 etc the most probable
position of finding the second atom of the diatomic molecule approaches the limit (or extremes)
of the Morse curve. The diagram below for energy versus the internuclear distance gives the
plots for the probability distribution (proportional to | | where represents the wave
function for the vibrational quantum number ):

(Diagram from Fundamentals of Molecular Spectroscopy by Banwell and McCash)

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

Internuclear distance
https://chem.libretexts.org/@api/deki/files/9100/wiki_figure_2.jpg?revision=1&size=bestfit&
width=361&height=656

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https://lh3.googleusercontent.com/proxy/kD87XHrvGYOo_A3My6ZmCa0LvJMN215CgUE
djbhu6yD4ANjAOVUq-aAMEe08_aTBz-
5mRZgfVBYs3Wfn1fjSDeOOtxX8QHjJoE2bd7PXEcGjzk2YB5A9VslCDqV_RJwH8PzN

Note: In both the above diagrams the lower vibrational states within the lower electronic energy
level should be

If a diatomic molecule undergoes a transition from a lower electronic state, ε΄΄ to a higher
electronic state, ε΄ then the higher excited state (represented here as ε΄) could either be a stable
excited state or an unstable excited state.

The diagram below illustrates the Morse potential energy curves for the ground state (electronic
state ε΄΄; vibrational states = 1,2,3 ….) and excited state (electronic state ε΄; vibrational
states = 1,2,3 ….)) and the corresponding - progressions for the four situations (a), (b),
(c) and (d):

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

(Diagram from Fundamentals of Molecular Spectroscopy by Banwell and McCash)

If the excited electronic state corresponding to the quantum number is a stable excited state
then any of the following situations can exist:

(a) stable state with the same internuclear distance;

(b) stable state with the internuclear distance slightly less than the ground state;

(c) stable state with the internuclear distance slightly greater than the ground state;

(d) stable state with the internuclear distance much greater than the ground state.

In accordance with the Franck Condon principle stated above, the transition must occur
vertically, i.e. there must be no change in internuclear distance.

Hence for a stable excited state as in (a), the most intense line in the - progression will be
the (0,0) line. However as is evident from the probability distribution plots, quantum theory
suggests that the highest probability of finding the second atom of the diatomic molecule is
near the equilibrium internuclear distance but there is a finite probability of the second atom of
this diatomic molecule existing at ‘other’ positions of the internuclear distance as well. Hence,
there is some chance of the transition originating towards the extremes of the =0

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

vibrational state and ending at the vibrational states = 1, 2, 3 … The intensity of the
(1,0) (2,0) lines will decrease rapidly.

If the stable excited state is as in (b) or (c) the most intense line in the − progression will
be the (2,0)line.

In general, the transitions occur such that they are ‘vertical’, i.e. there is no change in the
internuclear distance.

If the stable excited state is as in (d), the transition to the vibrational quantum number, ,
could be to a value close to (discussed in vibration/IR spectroscopy done earlier) which
is near the dissociation limit resulting in the molecule dissociating and hence the spectrum
showing as a continuum. The lowest wavenumber of this continuum is called the continuum
limit, ̅

The diagram below, which is a plot of energy versus internuclear distance again, is a more
detailed version of a stable excited state with the internuclear distance much greater than the
ground state (case (d) of the previous diagram). Here represents the dissociation energy for
the ground state and represents the dissociation energy of the excited state.

represents the excitation energy of the products formed after dissociation. As mentioned
earlier and is evident from the previous diagram, the spectrum of this consists of some
vibrational transitions (quantized) followed by a continuum which represents non-quantized
transitions since the diatomic molecule has dissociated. The lower wavenumber limit of this
continuum, ̅ represents just sufficient energy for dissociation. Hence:

̅ = { + }

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

(Diagram from Fundamentals of Molecular Spectroscopy by Banwell and McCash)

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Ma
ps/Map%3A_Physical_Chemistry_(McQuarrie_and_Simon)/13%3A_Molecular_Spectroscop
y/13.06%3A_Electronic_Spectra_Contain_Electronic_Vibrational_and_Rotational_Informati
on

: dissociation energy

: depth of the potential of the ground electronic state,

: difference in energy of the minima of the two electronic potential energy curves, lower
being and the higher being

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

Close to the dissociation limit, the value of ∆ for any two successive vibrational levels,
and ( + 1) is:

∆ = ( ) − = {1−2 ( + 1)}

At high values of the vibrational quantum number, v, ∆ → 0, hence:

{1−2 ( + 1)} ≈ 0 , i.e. ≅( − 1).

If the value of is known then can be evaluated. From this the approximate
dissociation energy for the molecule can be evaluated.

For a more accurate value of the dissociation energy, the Birge and Sponer plot can be used.
For low values of the vibrational quantum number successive vibrational energy levels have a
greater separation in terms of energy. As the vibrational quantum number increases, the value
of ∆ decreases. Birge and Sponer suggested that since the dissociation energy is a sum of
all the successive values of ∆ from = to = , a graph of ∆ (for successive
energy levels) versus the vibrational quantum number could be plotted. The graph would be a
decreasing curve. The area under the curve would then give a value of the dissociation energy.

https://media.springernature.com/lw785/springer-static/image/chp%3A10.1007%2F978-3-
319-23252-2_3/MediaObjects/336936_1_En_3_Fig1_HTML.gif

Note: In the above figure, ∆ ( ) on the y-axis is the same as ∆ and on the x-axis is the
vibrational quantum number, . The point on the x- axis marked is the same as

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

Rotational fine structure:

The rotational fine structure appears as a series of lines within the vibrational coarse structure
of the electronic transition. This implies that if the lines in the -progression are clearly
resolved then they will now have a cluster of closely spaced lines due to the rotational
transitions. If the resolution is not good then these lines may appear as a broad band within the
-progression.

As mentioned earlier,
={ + + }

where , and are once again the electronic, vibrational and rotational quantum numbers
respectively and the energy is in units of wavenumber / .

The change in energy due to the transitions:

∆ = {∆ + ∆ + ∆ }

i.e.
∆ = {( − )+ ( − )+ − }

For the rotational fine structure:

∆ = {∆ + ∆ }+ ∆

∆ = {∆ + ∆ } + ∆{ ( + 1)}

If is the rotational constant corresponding to the rotational state (lower electronic level
) and is the rotational constant corresponding to the rotational state (higher electronic
level ), then:

∆ = { ( + 1) − " ( + 1) }

Usually ≠ "; if a bonding electron is excited then the bond becomes weaker. This implies
that the internuclear distance increases and in turn I increases. Due to an increase in
, the rotational constant decreases, i.e. < ". If an antibonding electron is excited, the
bond order increases. This implies that the internuclear distance decreases and in turn I
decreases. Due to an decrease in , the rotational constant increases, i.e. > ".

Transitions between the rotational energy levels and follow a set of selection rules. To
understand the symbols used in these selection rules, it is important to understand the
classification of the electronic states and the symbols used to represent these states.

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

For example consider the simple diatomic molecule hydrogen H2.

The molecule has two electrons; one contributed each from the individual hydrogen atoms. In
the ground state the two electrons will occupy the same molecular orbital 1 and hence the
electronic configuration for the molecular orbital will be 1 . In accordance with Pauli’s
Exclusion Principle, the two electrons will have opposing spins, i.e. +½ and − ½.

To represent this ground state, the following symbols are to be understood:

 The orbital angular momentum of each of the constituent electrons (represented

by ) in the atomic state (1 ) is zero, i.e. = 0 for each of the two
electrons.
 In the diatomic molecule, the internuclear axis is taken as the reference
direction. The axial component (along the axis) of the orbital angular
momentum is represented as .
 This axial component, , takes either positive integral values or is zero, i.e.
= | |. Here is zero for each of the two electrons.
 The state of the electron is designated by Greek symbols (σ, π, δ, φ….) similar
to the atomic states s, p, d, f…..
 The total orbital angular momentum, represented by , is the summation of the
value of for each of the ith electrons, i.e. = ∑ , where the subscript i
is the electron index.
 In this example = 2, therefore = 0 + 0 = 0.
 Depending on the value of total orbital angular momentum, , the states are
designated by Σ, Π, Δ, Φ corresponding to = 0, 1, 2, 3 …. Here = 0, which
implies Σ - state.
 The spin angular momentum of the electrons (represented by or ) in an
atom is represented by the same symbol in molecules.
 The total spin angular momentum, (represented by S for atoms), is similarly the
summation of the value of for each of the i electrons, i.e. = ∑
where i is the electron index. For molecules, S is represented by , i.e.
≡ . Hence = ∑ .
 In this example = 2,therefore = (+½) + (−½) = 0
 The multiplicity of a molecular state is (2 + 1). Here the multiplicity is 1 since
= 0.
 If the multiplicity is 1, the state is called a singlet state; if the multiplicity is 3,
the state is called a triplet state, etc.
 The total electronic angular momentum, represented as , will have
contributions from both the total orbital angular momentum, , and the total
spin angular momentum, , i.e. = + .
 The term symbol for the molecular state is (2 Σ +1)
 In this example, = 0 + 0 = 0.

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

 The state of this system (hydrogen molecule, H2) is written as 1Σ where the
upper (left hand side) prefix is equal to the multiplicity of the state.
 Σ states are divided according to the symmetry operation, reflection, about the
plane of symmetry which is a plane drawn through both nuclei. If represents
the wave function of the state and remains unchanged by the operation of
reflection about this plane, then the state is labelled as Σ+ (symmetric). If
changes sign by the operation then the state is labelled as Σ- (anti-symmetric).
 For hydrogen molecule then the ground state which is is 1Σ+.
 The electronic configuration for this ground state molecular orbital for H2 is
1 .
 Thus the ground state of molecular hydrogen is classified (written) as 1Σ+g.

Selection rules for the rotational fine structure:

The selection rule for the rotational quantum number depends on the type of electronic
transition i.e the → transition occurring in the molecule:

 ∆ = ±1 for 1Σ → 1Σ transitions.
 ∆ = 0, ±1 for all other transitions; however the = 0 to = 0 transition is
forbidden.

Hence for the electronic transitions between 1Σ states only the P- and R- branches occur while
for all other electronic transitions the Q-branch will also occur.

P-branch ⇒ ∆ = −1, i.e. = ( + 1)

∆ = { ( + 1) − " ( + 1) } = { ( + 1) − "( + 1)( + 2) }

={ ( + )− "( + 3 + 2)} = { ( + )− "( + 2 + 1) − "( + 1) }

= { ( + 2 +1− − 1 ) − "( + 1) − "( + 1) }

= { ( + 1) − ( + 1) − "( + 1) − "( + 1) }

= {( − ") ( + 1) – ( + ")( + 1) } where = 0,1,2 … ..

R-branch ⇒ ∆ = +1, i.e. = ( " + 1)

∆ = { ( + 1) − ′′ ( + 1) } = { ( + 1)( + 2) − ′′ ( + 1)}

={ ( + 2 +1+ + 1 ) − ′′ ( + 1)}

={ ( + 2 +1+ + 1 ) − ′′ ( +2 + 1) + ′′( + 1) }

={ ( + 1) + ( + 1) − ′′( + 1) + ′′( + 1) }

= {( − ′′) ( + 1) + ( + ′′)( + 1) } where = 0,1,2 … ..

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

Combining the equations:

∆ = {( + ′′) ( + 1) + ( − ′′) ( + 1) }

where = 0,1,2 ….and = +1 for R-branch and = −1 for P – branch.

Q-branch ⇒ ∆ = 0, i.e =

∆ ={( − ′′′) + ( − ′′) }

Or

∆ ={( − ′′) + ( − ′′) }

where = 1,2,3 … and ≠ 0 as the 0 → 0 transition is forbidden

Each of the above equations representing the P,Q,R branches are equations of a parabola.
Together these are referred to as the Fortrat parabolae. The diagram below shows the
Fortrat parabolae – the y- axis here represents values of ( + 1).

(Diagram from Fundamentals of Molecular Spectroscopy by Banwell and McCash)

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

Predissociation:

When a large number of vibrational transitions occur in a molecule, the vibrational coarse
structure and rotational fine structure are rather distinct in the - progression for lower values
of and again for higher values of but the fine structure is blurred in the intermediate values
of . Blurring of a spectrum can occur either because of dissociation or due to insufficient
resolution. Since some regions of the - progression are clearly resolved these are not the
reasons. This blurring of the spectrum for intermediate values of is referred to as
predissociation.

https://www.researchgate.net/profile/Azhar_Iqbal9/publication/49299883/figure/fig2/AS:669
457760411671@1536622576324/Diagram-representing-the-predissociation-mechanism.ppm

Predissociation occurs when two excited Morse curves for a particular molecule have
comparable energy and intersect – one of these Morse curves represents a stable excited state
whereas the other represents an unstable excited state. If a transition occurs from the =0
state to the higher vibrational states ( values) close to the intersection, then a possibility exists
of the excited molecule ‘crossing over’ to the unstable excited state and hence dissociating.
The transitions to levels beyond the point of the intersection of the stable and unstable
excited states continue to show as resolved lines in the - progression.

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

(Diagram from Fundamentals of Molecular Spectroscopy by Banwell and McCash)

A diagrammatic illustration of this phenomenon is as above.

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

Electronic spectra of polyatomic molecules:

For most polyatomic molecules, particularly in the liquid state, both the vibrational “coarse”
structure and the rotational “fine” structure cannot be resolved. Also as discussed (earlier in
Group vibrational frequencies), bond and functional group properties are largely independent
of the surrounding atoms in a molecule. This implies that all those molecules with the same
functional group, e.g. alcoholic, amino, nitro, aldehydic, acidic, etc will display a typical
functional group electronic transition and hence can be identified by the presence of this peak
in the electronic (ultraviolet and visible) spectrum. The position and intensity of the rather
broad absorption maxima due to the electronic transition is always characteristic of the
functional group present in the molecule.

Transitions between the electronic energy levels occur according to the following rules:

1. ∆ = 0, ±1 ; hence transitions like Σ↔Σ, Σ↔Π, Π↔Π are permitted. However, Σ↔Δ
is forbidden.
2. ∆ = 0 (or ∆ = 0); hence singlet state to singlet state transition is allowed but singlet
state to triplet state transition is forbidden.
3. Based on the above two points, ∆ = 0, ±1.
4. From symmetry considerations:
 Σ+ ↔ Σ+ and Σ- ↔ Σ- are allowed, but Σ+↔ Σ- are forbidden.
 ↔ is allowed, but ↔ and ↔ are forbidden.

Electronic spectra usually exhibit a broad absorption maxima corresponding to a specific

value of ∆ , characterised by a typical value (or position) of . This enables
the identification of the molecule/molecular structure/presence of a functional group.

The ultraviolet (UV) and visible range of the electromagnetic radiation is divided into three
categories:

 < 200 nm far or vacuum ultraviolet

 200 to 400 nm near ultraviolet
 400 to 700 nm visible

Electrons in most molecules fall into one of the following three classes: σ electrons, π electrons
and non-bonding electrons (designated as n). Usually σ electrons are most firmly bound to the
nuclei and hence require most energy (highest value of frequency or wavenumber, lowest value
of wavelength) for the electronic transition. The π and n electrons mostly require lower energy
than σ electrons. In terms of molecules, a single bond between atoms, e.g. C ̶ C, C ̶ H, O ̶ H etc
contains only σ electrons, a multiple bond C = C, C = N, C ≡ C etc contains π electrons in

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

addition to σ electrons. Functional groups containing N, O, halogens possess n electrons along

with σ and π electrons. Hence a molecule e.g. aniline (C6H5NH2) contains σ, π and n electrons.
The molecular formula and structure decides which of the σ, n, π electrons will (or can) be
involved in the electronic transitions. Each type of electronic transition corresponds to a
different value of ∆ . In all compounds, apart from alkanes, electrons can undergo
several possible transitions with different values of ∆ .

Based on the above set of selection rules for the electronic transitions, the following transitions
are allowed in various molecules:

 σ → σ* (* indicates antibonding molecular orbital) – in alkanes

 π → σ*
 n → σ* ( n indicates a nonbonding molecular orbital) – in compounds containing O,
N, S
 σ → π* (* indicates antibonding molecular orbital) – in carbonyl compounds
 π → π* - in alkenes, carbonyl compounds, alkynes, azo compounds
 n → π* – in carbonyl compounds

The energy ordering of these transitions is:

σ → σ* > σ → π* ≥ π → σ* > π → π* ≈ n → σ* > n → π*

 σ → σ* transitions usually occur at wavelengths < 200 nm (vacuum ultra violet region)
 n → σ* and π → π* usually occur at wavelengths in the range of 200 to 300 nm
(borderline of far and near ultra violet regions)
 n → π* usually occur close to and beyond 400 nm (near ultra violet and visible regions)

(Diagram from Fundamentals of Molecular Spectroscopy by Banwell and McCash)

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

The allowed electronic transitions mentioned above are shown in the hypothetical energy level
diagram below:

http://www.chem.ucla.edu/~bacher/UV-vis

Some values of :

(Data from Fundamentals of Molecular Spectroscopy by Banwell and McCash)

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

Values of for oxygen-containing molecules where both the π → π* and n → π* transitions

occur:

(Data from Fundamentals of Molecular Spectroscopy by Banwell and McCash)

In p-benzoquinone (last molecule listed above), the value of for the n→π* transition has
shifted to the visible region due to conjugation. 435 nm falls in the blue region of the visible
spectrum and hence the compound is yellow in colour.

(Diagram from Fundamentals of Molecular Spectroscopy by Banwell and McCash)

From the above spectrum, which exhibits a broad absorption maxima, it is evident that the
value of λ for the n→π* transition in propanone appears at approximately 275nm.

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

The intensity of the broad absorption maxima follows the Beer- Lambert - Bouger Law.

Lambert’s Law:

Equal fractions of the incident radiation are absorbed by successive layers of equal thickness
of the light absorbing medium. If I represents the intensity of the radiation, dI the change in
intensity due to the absorption and dl the thickness of the medium, then:

⍺ ; = ⍺

where α is the constant of proportionality and is called the absorption coefficient.

This law can also be stated as follows:

The rate of decrease of intensity with thickness of the absorbing medium (i.e. ) is proportional
to the intensity of the radiation. Hence,

⍺ I or = ⍺I

where ⍺ is the constant of proportionality and is called the absorption coefficient.

Beer’s Law:

The value of the absorption coefficient, ⍺, is directly proportional to the molar concentration,
, of the sample (solution) as long as the solution is dilute.
Hence ⍺ ⍺ or ⍺ = , where is the constant of proportionality.

Combining the above mathematical expressions:

= or = .

Integrating within the limits – intensity of the incident radiation and intensity of the
transmitted radiation:
ln = ( is path length, usually in units of cm)

( ’ )
=
.

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

( ’ )
=
.

or
=( ) ,
where is called the molar extinction coefficient and is given by:
= L mol-1 cm-1

Absorbance, is hence =

Beer-Lambert-Bouguer Law:
Absorbance, is proportional to path length and to the molar concentration.

The units of the molar extinction coefficient are: ( ) ( ℎ) , i.e.

( ) or . Converting to or to , i.e to 10 and
1
to 10 or 10 , the unit will be equivalent to 10 .
Absorption bands with values > 10 are labelled as strong/high intensity bands.
A high value of , implies a low value of the transmitted intensity, I. This means that most of
the incident radiation is absorbed by the sample which means that the transition probability for
this particular electronic transition is high. (Occasionally tables in literature/texts give
values and not values of ). Usually transitions follow the selection rules but sometimes
“forbidden” transitions also appear. However, the intensity of these lines/bands is low, i.e.
value is low.

The intensity of the absorption can also be represented in terms of transmittance, T.

Transmittance is defined as the ratio of the intensity of the transmitted radiation to the intensity
of the incident radiation. = . Hence the absorbance, = .

Values of (units nm) and ε (units ) for different “lengths” of carbon-carbon

bonds:

(Data from Fundamentals of Molecular Spectroscopy by Banwell and McCash)

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

As conjugation increase the value of increases.

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

The absorption of visible or ultraviolet radiation is due to the excitation of electrons, however
the nuclei that the electrons hold together (the nuclei that are bonded together by the electrons
involved in the bond formation) determine the exact value of for a particular
compound/molecule. This is because the properties of the nuclei (e.g. electronegativity of the
the atom) determine the “strength” which holds the electrons together and hence influence the
energy spacing between various molecular orbitals (e.g. HOMO and LUMO). In the above
energy level diagram the HOMO is n while the LUMO is π*. The characteristic energy of a
transition and hence the wavelength of the visible or ultraviolet radiation absorbed by a
molecule are a property of the group of atoms which constitute the functional group and not
the electrons alone. The groups of atoms causing an absorption of the incident radiation is
called a chromophore. The word literally means “bearer of colour”. It is defined as an isolated
covalently bonded group that displays a characteristic absorption in the ultraviolet/visible
spectrum. Structural changes within a particular chromophore change the exact energy and
intensity of the absorption maxima. Hence an amino group in an aliphatic amine will exhibit
specific values of and . This value will be different from the amino group in an aromatic
compound. Both the values could be close but are not identical. When the C=O group is present
in any compound, an absorption at about 290nm corresponding to the n → π* transition is
observed; the C=O is called a chromophore.

The attachment of a substituent in place of H on a basic chromophore changes the value of

and . The substituent usually does not give rise to a transition on its own but its presence
in the chromophore alters the value of (and ε). For example in the table below, one
aromatic proton (H) on the benzene ring has been replaced by the hydroxyl group in phenol
and the amino group in aniline. The value for the same transition (π→π*) has changed.
Substituents that increase the intensity of the absorption are called auxochromes. Usually, the
value of increases due to the presence of the auxochrome. Hence the auxochrome is also
called a colour enhancing group. Typical auxochromes are methyl, hydroxyl, alkoxy, halogen
and amino groups. Auxochromes can be acidic or basic, e.g. -OH and -NH2 respectively.

Compound/ Molecular / nm Molar extinction

formula coefficient, ε /
Benzene, C6H6 255 230
Phenol, C6H5OH 270 ≈620
Aniline, C6H5NH2 280 1430

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

The table below gives the changes that occur when the H in methane (CH4) is substituted by
another atom (e.g. Cl, I) or a functional group (e.g. hydroxyl -OH, amino –NH2):

Compound Intensity or values of ε / Transition with lowest

− energy
/nm
CH4 122 intense σ→σ*(C-H)
CH3CH3 130 intense σ→σ* (C-C)
CH3OH 183 200 n→σ* (C-O)
CH3SH 235 180 n→σ* (C-S)
CH3NH2 210 800 n→σ* (C-N)
CH3Cl 173 200 n→σ* (C-Cl)
CH3I 258 380 n→σ* (C-I)

Bathochromic shift (Red shift):

This is defined as the shift of towards higher values (increase in wavelength, i.e. towards
the red region of the electromagnetic spectrum) due to a change in solvent medium or due to
the presence of an auxochrome. For example, in an alkaline medium, p-nitrophenol shows a
red shift; the value of changes from 255nm (for pure p-nitrophenol) to 265nm (for p-
nitrophenol in an alkaline medium or solvent). Increased conjugation (alternate single and
double bond) also causes an increase in the value of . This is illustrated in the following
table:

Compound/ Molecular formula / / nm Molar extinction coefficient,

structure /
Ethylene (or ethene), C2H4, H2C = CH2 165 15 x 102
Butadiene,C4H6, 217 21 x 102
H2C = CH ̶ CH = CH2
Hexatriene, C6H8, 250 35 x 102
H2C = CH ̶ CH = CH ̶ CH = CH2

Hypsochromic shift (Blue shift):

This is defined as the shift of towards lower values (decrease in wavelength, i.e. towards
the blue region of the electromagnetic spectrum) due to a change in the solvent medium or due
to the removal of or decrease of conjugation. For example, as mentioned above, aniline has an
absorption maxima at 280nm; if acid is added the anilinium ion, C6H5NH3+ is formed which
has an absorption maxima at 254nm.

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

Hypochromic effect:

This is defined as a decrease in absorption intensity due to a structural change in the molecule.
For example the decrease in the absorbance of ultraviolet light in a double stranded DNA
compared to its single stranded counterpart.

Hyperchromic effect:

This is defined as an increase in absorption intensity due to a structural modification in the

chromophore. Hence if a change in the functional group leads to an increase in the molar
extinction coefficient, ε, for a particular chromophoric group it is said to have brought about
a hyperchromic effect. For example:

Compound Benzene Aniline

/ nm 255 280
Molar extinction coefficient, 230 1430
ε/

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

Since electronic transitions involve the absorbance of energy, the observer will perceive the
complementary colour and not the colour that has been absorbed. Compounds which exhibit
electronic transitions in the visible region will be coloured and display the complimentary
colour. A table of λmax and the observed/perceived colour is:

Light absorbed Colour observed/displayed

Colour Wavelength, / nm
Violet 400 Yellow
Blue 450 Orange
Blue-green 500 Red
Yellow-green 530 Red-violet
Yellow 550 Violet
Orange-red 600 Blue-green
Red 700 Green

A colourful and pictorial illustration of colours is given below:

http://www.chem.ucla.edu/~bacher/UV-vis

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

Free Electron Molecular Orbital (FEMO) or Free Electron model

This is an important application of the particle in a one-dimensional box problem. This model
is used mainly to calculate λmax values for polyenes. Polyenes are long-chain hydrocarbons with
alternate single and double carbon – carbon bonds, i.e. conjugation. Although, polyenes are not
linear molecules, it is assumed here for simplicity, that they are linear molecules. The labile π-
electron in the polyene identifies with the mobile particle in a one-dimensional box. The
constant potential of the one-dimensional box is provided by the σ – bonds of the polyene. The
length of the constant potential well, i.e. the ‘length’ of the box may be taken as the end-to-end
length of the polyene.

For example butadiene, C4H6, H2C = CH ̶ CH = CH2 has 4 carbon atoms, 4 π-electrons, 2
double bonds and one single bond. Since the π-electrons are labile (constantly in motion) the
butadiene molecule can be considered to have 3 identical carbon-carbon bonds each having
partial single and partial double bond character.
The end-to-end length of the molecule could then be considered as:
3 x (length of a carbon-carbon bond having partial single and partial double bond
character) = 3 x 145pm = 435pm.
However, the constant potential provided by the σ – electrons does not vanish at the ends
(extremes) of the molecule. The length of the constant potential well is considered to be
extending half a carbon-carbon bond length on each side of the molecule.
For butadiene, the ‘length, L’ of the box, and hence the distance that the potential remains
constant, is then:
3 x (length of a carbon-carbon bond having partial single and partial double bond
character) + 145pm = 4 x 145pm = 580pm.

There are 4 π-electrons. In accordance with Aufbau Principle and Pauli’s Exclusion Principle,
each molecular orbital (MO) can have a maximum occupancy of 2 (one electron with spin +1/2
and the other with spin -1/2).
Hence, in butadiene the HOMO is n = 2 and the LUMO has n = 3.

Following the particle in a box problem, the expression of energy, ,

ℎ
=
8
where the mobile π-electron is considered to be the particle. Hence mass of the electron, is
considered.

When the electron gets excited, the change in energy, ∆E is:

∆ = − =

This ∆E has units of J (Joule). From this the value of for butadiene can be calculated.

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

In general a polyene which has 2 carbon atoms has 2 π- electrons. These 2 π- electrons
occupy molecular orbitals such that the HOMO is and the LUMO is ( + 1).

The change in energy, ΔE for the transition HOMO → LUMO is :

( )
∆ = ( ) - =
where L = 2 x (length of a carbon-carbon bond having partial single and partial double
bond character)

For the straight chain conjugated polyene having 2 carbon atoms, there will be (2 − 1)
carbon-carbon bonds each having partial single and partial double bond character. However,
the constant potential well extends half a carbon-carbon bond length on each side of the
molecule. Hence to calculate the ‘length, L’ of the molecule 2 will need to be multiplied by
the length of a carbon-carbon bond having partial single and partial double bond character.

From the value of ∆ which has units of J (Joule), the value of for a particular molecule
can be evaluated.

From the above expression it is clear that as the ‘length, L’ of the polyene increases, i.e.
conjugation increases, the value of ∆ decreases. However, a low value of ∆ in J implies a
high value of the wavelength, λ. This explains the colour of large organic molecules which are
used as dyes, e.g. azo dyes (shades of yellow, orange, rust, red) and indigo (shades of blue).

Carrots contain a long chain polyene, β-carotene, which has 11 double bonds and 22 π-
electrons. Due to the increased conjugation, the value of is 475nm. This falls in the visible
region at the blue end of the electromagnetic spectrum and hence carrots display
orange/red/purple colour depending on the exact structure of the organic molecule present in
the carrots!

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

https://chem.libretexts.org/@api/deki/files/121539/Figure_1.gif?revision=1
Compound Ethylene Butadiene Hexatriene Octatetraene β -carotene
Number of π electrons 2 4 6 8 22
/nm 165 217 250 300 465
2 2 2
Molar extinction coefficient 15 x 10 21 x 10 35 x 10 ≈ 42 x 10 125 x 102
ε/

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tbn0.gstatic.com/images?q=tbn%3AANd9GcRRaYEJg2zo4n6guNjI9yFl15ZskAM4r0-
Emg&usqp=CAU

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

https://i.pinimg.com/originals/11/b2/40/11b24048191f0ac67e4f4f42e17f1cdd.jpg

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

Primary and secondary processes:

A molecule can undergo a primary process of absorption of energy from the incident
electromagnetic radiation by undergoing an electronic transition ( " → ). After it exists in
an excited electronic state it can return to the ground state by various secondary processes.
These secondary processes are:

 Dissociation
 Re-emission
 Flourescence
 Phosphorescence
 Stimulated emission – the beginning of lasers.

As mentioned above the secondary processes that can occur after the initial primary process
of excitation involve, among other possible processes, fluorescence (F) and phosphorescence
(P). Both these processes are spontaneous emissions of electromagnetic radiation. The time
scales are very different. Fluorescence is a ‘fast’ process which stops immediately as the source
of radiation is removed, while phosphorescence is a ‘slow or delayed’ process.
The emitted radiation has longer wavelength/lower energy than the absorbed light/radiation
since a part of the initial energy absorbed has already been released by a non-radiative process.
Hence an emission in the longer wavelength, i.e. in the visible part of the spectrum can be
achieved with non-visible UV radiation.

The diagram on the right illustrates the initial electronic

excitation and the subsequent process of fluorescence
(F). At normal temperatures essentially all molecules
will exist in the electronic ground state and within that
in the ground vibrational state (zero level). The Franck-
Condon principle requires that excitation occurs by a
vertical transition, shown by the red line, resulting in the
population of higher vibrational levels in the excited
state. After the initial primary process (A), several
events may take place.

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

1. The vibrational energy may be lost as heat, relaxing the excited state to its zero
vibrational level, i.e the lowest vibrational level within the excited electronic state.

2. The excited state may then return to the ground state by emitting a photon.
If this happens from the zero vibrational level the frequency or energy of the emitted
light will be lower than that of the initially absorbed light. This radiative decay is
called fluorescence (F) and takes place rapidly from the initial excited state. The
process can be represented as follows:

S0 + ℎ → S1 → S0 + ℎ (Fluorescence) (Note: < )

If the radiative decay occurs slowly by way of other excited states, it is

termed phosphorescence (P). These processes are explained in the Jablonski diagram
below:

https://chem.libretexts.org/@api/deki/files/73601/jablonski.gif?revision=1

As shown in the diagram, it is possible that more than one electronic excited state is likely to
exist for a given molecule, six excited states are drawn and labelled in the diagram. Excited
states may be classified as singlet (S) or triplet (T) based upon their total electron spin angular
momentum ( or ) and their multiplicity [(2 + 1) or (2 + 1)].

The electrons in most non-metallic organic compounds are paired (opposite spins) in bonding
and non-bonding orbitals, resulting in a net zero spin for the molecule in the ground state. Such
states are called singlets, i.e. (2 + 1) or (2 + 1) is one, where is the total spin evaluated

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

as . The singlet states have been labelled S0 (ground state) and the excited states as S1, S2,
S3….

The triplet states, i.e. (2 + 1) or (2 + 1) is three, are all excited states and have been
labelled as T1, T2, T3….As is evident from the figure, the excited triplet state T1 is lower in
energy than the excited singlet state S1. In a singlet excited state the electrons have opposite
spins and hence their magnetic moments attract each other increasing the inter-electron
repulsion between them. In the triplet excited state, the electrons have parallel spin and hence
their magnetic moments repel each other; this minimises the inter-electron repulsion, resulting
in the triplet state having lower energy than the singlet state. Each electronic state will have a
group of vibrational (and rotational) states, depicted by light blue lines above each state.
Transitions between electronic states often occur to higher vibrational levels which then relax
to lower levels by collisional loss of heat (translational energy).

The distinction between singlet and triplet states is important because in accordance with the
selection rules for electronic transitions (done earlier) the photon induced excitation always
leads to a state of the same multiplicity, i.e. singlet to singlet or triplet to triplet. Since most
ground states are singlets, this means that the excited states initially formed by absorption of
light must also be a singlet. Internal conversion (IC) of excited states to lower energy states
of the same multiplicity takes place rapidly with loss of heat energy (relaxation). During the
process of internal conversion, the electron retains its original spin. Conversion of a singlet
state to a lower energy triplet state is termed intersystem crossing (ISC). This process is
slower than internal conversion. Intersystem crossing hence involves the reversal of the
electron spin. The process of intersystem crossing is “spin-forbidden” but does occur due to
“spin-orbit coupling”. Radiative decay from a triplet state is called phosphorescence (P) and
is generally quite slow. Once in the triplet state, de-excitation to the ground singlet state is
again “spin-forbidden”. Consequently, the molecule “stays” in the triplet state for a
considerably longer period of time than it would otherwise. When the emission finally occurs,
it is in the form of phosphorescence. Phosphorescence usually occurs for compounds which
have “heavier nuclei” since the spin has to be reversed by the process of “spin-orbit coupling”.
The above process of phosphorescence can be represented as:

S0 + ℎ → S1 →T1 →S0 + ℎ (Phosphorescence) (Note: < )

where ℎ represents the initial primary process. The other steps involve secondary processes.
The emitted radiation, ℎ , involves lower energy which implies the radiation has a longer
wavelength.

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

The approximate timescales for the transitions mentioned in the Jablonski diagram are given
in the following table:

Process Transition Time scale/s

Light Absorption (Excitation) S0 → Sn ≈ 10-15 (instantaneous)
Internal Conversion Sn → S1 10-14 to 10-11
Vibrational Relaxation Sn * → Sn 10-12 to 10-10
Intersystem Crossing S1 → T 1 10-11 to 10-6
Fluorescence S1 → S0 10-9 to 10-6
Phosphorescence T 1 → S0 10-3 to 100
S1 → S0 10-7 to 10-5
Non-Radiative Decay
T 1 → S0 10-3 to 100
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbo
ok

The non-radiative decay noted in the last row may take place by intermolecular energy transfer
to a different molecule. This collisional process is termed quenching.

Examples of fluorescence:
Fluorescence can occur in gaseous, liquid, and solid chemical systems.
 A fluorescence example could be when a 3s electron of a vaporized sodium atom is
excited to the 3p state by the absorption of a radiation at wavelength 589.0 nm. After
10-8 s, the electron returns to ground state and on its return it emits radiation at 589.6nm.
 Fluorescence due to a  * →  transition is seldom observed.
 Fluorescence is usually associated with the less energetic * →  and
* → n transitions. The most intense fluorescence is found in compounds containing
aromatic functional groups.
 Compounds containing aliphatic and alicyclic carbonyl structures or highly conjugated
double-bond structures may also exhibit fluorescence.
 Most unsubstituted aromatic hydrocarbons exhibit fluorescence in solution.
 Fused ring structures, e.g. quinolone C9H7N, tend to show fluorescence.

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

Examples of phosphorescence:
Everyday examples of phosphorescent materials are the glow-in-the-dark toys, stickers, paint,
wristwatch and clock dials that glow after being charged with a bright light such as in any
normal reading or room light. Typically, the glow slowly fades out, sometimes within a few
minutes or up to a few hours in a dark room. Common pigments used in phosphorescent
materials include zinc sulphide and strontium aluminate. Zinc sulphide has been used since the
1930s. Currently, strontium aluminate, with a luminance approximately 10 times greater than
zinc sulphide is commonly used. Strontium aluminate based pigments are now used in exit
signs on roads/highways, pathway marking, and other safety related signage.

Chemiluminescence involves the emission of light during a chemical reaction; it does not
produce significant quantities of heat.
 One of the oldest known chemiluminescent reactions is that of elemental
white phosphorus oxidizing in moist air, producing a green glow. This is a gas-phase
reaction of phosphorus vapour, which occurs above the solid, with oxygen producing
the excited states (PO)2 and HPO.
 Chemiluminescence has been applied by forensic scientists to solve crimes.
The iron from blood acts as a catalyst and reacts with luminol (C8H7N3O2)
and hydrogen peroxide to produce blue light for about 30 s.
C8H7N3O2 + H2O2 → 3-Aminophthalate (excited) →3-Aminophthalate + light
The decay of the excited state to ground state is accompanied by the emission of light.
Since only a small amount of iron, present in the haemoglobin in blood, is required for
the test, trace amounts of blood can be detected by this test.

Chemiluminescence differs from fluorescence or phosphorescence in that the electronic

excited state is the product of a chemical reaction rather than of the absorption of a photon. It
is the antithesis (opposite) of a photochemical reaction. In a photochemical reaction, light is
used to initiate a chemical reaction. In chemiluminescence, light is generated from a
chemically exothermic reaction.
When chemiluminescence takes place in living organisms, the phenomenon is
called bioluminescence. Hence, bioluminescence involves light emitted by a microorganism
in the course of metabolism. A common example of bioluminescence in nature is the
firefly. Fireflies are also known as lightning bugs. They have a special organ that
produces light through a chemical reaction. Fireflies use flashing light to attract mates, but
begin emitting light even as larvae.
Deep sea organisms produce light to lure and catch prey, to camouflage themselves, or to attract
others.
Some bacteria even use bioluminescence to communicate.
The common colours for the light emitted by these animals/organisms are blue and green
because they have shorter wavelengths than red and can transmit more easily in water.

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Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

The phenomenon of the ‘northern lights’ observed in the atmosphere is due to the charged
particles from the sun striking atoms and molecules in the Earth’s atmosphere. The charged
particles impart energy to the molecules and excite them, causing them to ‘glow’. This
phenomenon occurs when large numbers of electrically charged particles (electrons) at high
speed stream in towards the Earth along its magnetic field and collide with the highest air
particles. The air then lights up rather like what happens in a fluorescent light tube. The
resulting colours reflect which gases are present there, the most usual yellow-green colour
coming from oxygen. Red colouring is also due to oxygen with a contribution from nitrogen.
The violet which is often seen at the lower edge of the aurora is due to nitrogen, as is most blue
colouring. The charged particles originate from the sun, and it is the 'weather' conditions on the
sun that decide whether or not the aurora can be observed. Particles can stream out from the
sun and some are captured by the Earth's magnetic field and find their way into the polar
regions.
https://www.tgo.uit.no/articl/nord_eng.html

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Physical Chemistry V – reading material only for students at Miranda House, University of Delhi 2021

MAGNETIC RESONANCE or SPIN RESONANCE SPECTROSCOPY

Nobel prizes associated with NMR spectroscopy:
Name Subject Year Area of research
O.Stern Physics 1942 Magnetic moment of the proton
I.I. Rabi Physics 1943 Resonance method for recording
magnetic properties of nuclei
F.Bloch and E.M. Physics 1952 Methods in nuclear magnetic
Purcell precision measurements
R.R.Ernst Chemistry 1991 Methods in HR-NMR
K.Wuthrich Chemistry 2002 NMR for 3D structures of
biological molecules
P.C.Lauterbur and Physiology/Medicine 2003 MRI technique
P.Mansfield

All electrons and some nuclei possess spin denoted by S in the former and I in the latter. For
electrons with a spin of ½, the magnitude of the spin angular momentum vector ⃗ is:

⃗ = ( + 1) ħ = √ ħ

Similarly, for nuclei which have a finite value of spin I,

⃗ = ( + 1) ħ

The nucleus consists of:

 protons which have a spin ½; mass 1.67 x 10-27kg and charge +1.6 x 10-19C
 neutrons which have a spin ½; mass 1.67 x 10-27kg and no charge.
Hence a nucleus consisting of protons and n neutrons has a charge + and a total spin which
depends on the vector addition of the spins of protons and neutrons, each having a
magnitude of ½. The laws governing the vector addition of and are somewhat ambiguous
and hence for a particular nucleus whose atomic mass is ( + ), the value of the nuclear spin
I depends on the following rules:

1. Nuclei with even values for both and have zero spin, i.e. I = 0 for 4He2, 12C6, 16O8.
2. Nuclei with odd values for both and have integral spin. For example 2H1, 14N7 have
I =1 and 10B5 has I = 3.
3. Nuclei with odd mass, i.e. ( + ) odd have half-integral spin. For example 1H1, 15N7,
13
C6 have I = ½ and 17O8 has I = 5/2.

The spin angular momentum vector (either ⃗ or ⃗ ) can have only certain specified directions
given by the quantum mechanical law mentioned earlier. Since I can either have integral or
half-integral values the allowed components are:

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Physical Chemistry V – reading material only for students at Miranda House, University of Delhi 2021

 If I is integral then only those components are permitted whose magnitude along the
reference direction (z - axis) are all integral, i.e.
= , ( − 1), ( − 2), … 1, 0, −1 … … − .
 If I is half-integral then only those components are permitted whose magnitude along
the reference direction (z - axis) are half-integral, i.e.
1 1
= , ( − 1), ( − 2), … + , − … … −
2 2
Therefore there are always a total of (2 + 1) components of the spin. These (2 + 1)
components are all degenerate.

For the electron, whose spin is half-integral (S = 1/2) the possible values are + , − .
However, as each of the above mentioned particles (nucleus or electron spin) is a spinning
charged particle it has a magnetic moment. Due to this finite magnetic moment the degeneracy
will get lifted in the presence of an external magnetic field.

Magnetic moment of a spinning charged particle:

The spinning of a charged particle is equivalent to the circulation of charge around the spinning
axis. This motion, produces a tiny magnet along the spinning axis. The magnetic moment µm
of this tiny magnet can be evaluated using Ampere’s law. According to this law:
µ = ,
where I is the current circulating per unit time and A is the area of cross-section, .
Consider an electron of mass me and charge –e orbiting in a circle of radius r. If T is the time
period of revolution, then:
−
=

If is the velocity associated with the movement of the electron, then T = .

Therefore, = and the magnetic moment, µ = = .

Multiplying and dividing by me,

µ = = ( )=

where L represents the angular momentum.

Hence the magnetic moment is proportional to the angular momentum.

The constant of proportionality is called the gyromagnetic ratio (or magnetogyric ratio) for the
electron, .

For the electron = .

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Physical Chemistry V – reading material only for students at Miranda House, University of Delhi 2021

https://lh3.googleusercontent.com/proxy/aoMuSHv1qf8BfpX8pzGkvbpSqTbRlQvkJ9EnZG0
n6gYTmNmP2bxJlW-vodheYWclzf8M9tm57Z59EGwZrkw5olwOdDn-
6jVI4_Xfwi_torHwQr0Zu24I74_ZANVs
The units of the gyromagnetic ratio are:
In general, the gyromagnetic ratio, is defined as the ratio of the magnetic moment to the
µ
angular momentum, i.e. = .

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Physical Chemistry V – reading material only for students at Miranda House, University of Delhi 2021

https://mriquestions.com/uploads/3/4/5/7/34572113/795540_orig.gif

For an isolated particle (or point charge) of mass m and spin I (e.g. a nucleus for which

≠ 0), the magnetic moment µm is proportional to ⃗ . If the charge on this particle is , then:

µ ⍺ ⃗

= ⃗

As mentioned earlier, the factor is the gyromagnetic ratio of this isolated particle.

µ = { ( + 1) ħ } = { ( + 1) }.

Since most particles are not isolated but have a local environment which effects the magnetic
moment, the local environment must be accounted for in expression for the magnetic moment.
For nuclei the local environment is taken into account by including a G-factor; for electrons
the local environment is taken into account by including a factor , called the Lande -factor.

Hence for a nucleus of mass , charge and spin existing in a local environment:
ℎ
µ = { ( + 1) }
4
If the nucleus has protons, then = + , where + is the charge on each proton.

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Physical Chemistry V – reading material only for students at Miranda House, University of Delhi 2021

Therefore, µ = { ( + 1) }

Multiplying and dividing by (mass of proton):

ℎ
µ = { ( + 1)}
4

= { ( + 1)}

= { ( + 1)}

Where is called the nuclear magneton, and is called the nuclear -factor.

= and = .

The nuclear magneton is a constant and has a value of 5.050 x 10 .

The nuclear -factor, has a particular value for a particular nucleus. For 1H, = 5.585.
For an isolated electron of spin S, mass me and charge = − :

µ = { ( + 1) ħ } = { ( + 1) }.

Taking into account the local environment of the electron in terms of the Lande -factor, :

µ = { ( + 1) } = − { ( + 1) }.

( ) ( )
where = is called the Bohr Magneton and = + , where S
( )
represents the total spin angular momentum, L represents the total orbital angular momentum
and J represents the total angular momentum for the sample; = +

The value of the constant is 9.273 x 10 .

For a system where L = 0 (i.e. total angular momentum = = 0), the value of S (i.e.
total spin angular momentum) is equal to the value of (i.e. total total angular momentum),
hence = + = 2.00.

Experiments conducted for the electron in a similar environment (i.e. when L = 0) have
assigned a value of 2.002319 to .

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Physical Chemistry V – reading material only for students at Miranda House, University of Delhi 2021

1
H Nuclear Magnetic Resonance Spectroscopy/ 1H NMR Spectroscopy:
Interaction between the nuclear spin and the magnetic field:
When a nucleus of magnetic moment is placed in a magnetic field (unit: Tesla, T), the
interaction energy, = - µ ⃗ • ⃗= − µ cos , where θ is the angle between the direction
of the magnetic moment and the external magnetic field, .

The magnetic dipole, will have different components along a reference direction. The
component of the spin angular momentum will govern the magnitude of the magnetic
moment. Hence, for nuclei: µ ⍺ or µ = .

The extent of interaction between a magnetic dipole, µ and an external magnetic field is
the scalar (or dot • ) product of the vectors µ and :

- µ ⃗ • ⃗= - µ cos
When the magnetic dipole is parallel to the external magnetic field, i.e. = 0 and cos = 1 ,
then the extent of interaction is − µ . This implies that the extent of interaction of the various
components of with the external magnetic field will be different, i.e. the degeneracy will be
lifted.

Hence for the 1H which has nuclear spin = ½ whose components of are ± ½ the
interactions with the external magnetic field will be different. This difference in interaction
of the two degenerate components with the external magnetic field results in the degeneracy
being lifted.

In the absence of the external magnetic field the two states are degenerate. In the presence of
the external magnetic field the degeneracy gets lifted. For the ‘up spin’ = +½, which is
aligned parallel to there is a decrease in energy, the magnitude of which is:

−µ = − =− .

For the ‘down spin’ = −½, which is aligned anti-parallel to there is an increase in energy,
the magnitude of which is:

−µ = − =− − .

The difference in energy between the two levels:

∆ = −{− } + {− − }=

(Note: An identical result for the change in energy will be obtained for nuclei with spin = 1.
The components of are ± 1, 0. In the presence of an external magnetic field the
degeneracy will be lifted giving rise to three levels. The change in energy, ∆ in accordance
with the selection rule ∆ = ±1 is once again .)

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Physical Chemistry V – reading material only for students at Miranda House, University of Delhi 2021

( = − )

( = + )

https://teaching.shu.ac.uk/hwb/chemistry/tutorials/molspec/nmrlev1.gif

https://www.jobilize.com/ocw/mirror/col11429_1.1_complete/m43551/Energy_States.png
The selection rule ∆ = ± 1 allows a transition between these two energy levels.
This allowed transition is induced by the incident electromagnetic radiation. For the transition
to be induced, the frequency, , of the incident electromagnetic radiation must ‘match’ the
frequency corresponding to this difference in energy ∆ . Hence the incident electromagnetic
radiation must ‘resonate’ with the external applied magnetic field,

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https://lh3.googleusercontent.com/proxy/QpJpxRT8cyrKlgLD9VW_1xaQjIDET9c5E8b2KM
KlSL4R35jYOMHxBABMqNg_a2h7I6LYsL5exo1B90q-dttQ2Y_p5ipc_l4ebKc9xkG-
3tYryN_3AU6VHHHnOuo

The frequency of the incident electromagnetic radiation is given by:

∆
= =
ℎ ℎ
For the 1H nucleus = 5.585. If = 100 , then = 2.3487T
(For the 1H nucleus, 42.6 ≡1 )

(Note: The magnetic moment is: = { ( + 1)}

or = ; i.e. =
{ ( )} { ( )}ħ ħ

The gyromagnetic ratio, is defined as the ratio of the magnetic moment to the angular
µ
momentum, i.e. = .

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Physical Chemistry V – reading material only for students at Miranda House, University of Delhi 2021

For a nucleus with spin , the gyromagnetic ratio will be:

µ
||
=
{ ( )}ħ

Hence can be represented as the gyromagnetic ratio, . The frequency of the incident
ħ
electromagnetic radiation can then be written as .

The energy ℎ = ℎ 2 = ħ .)

https://www.researchgate.net/profile/Kabindra_Kafle/publication/258167196/figure/fig2/AS:
613911678177312@1523379358764/Splitting-of-nucleus-spin-states-m-12-and-12-under-
the-influence-of-the-external.png

Note: In the above figure, the energy ℎ should actually be equal to = ħ

In the case of other nuclei for which > 1/2, the splitting pattern, in the presence of an external
magnetic field , is different and more energy levels are obtained in the presence of the
external magnetic field. However, at the elementary level, only single quantum transitions are
observed, i.e. the selection rule remains ∆ = ± 1. As mentioned earlier, for these single
quantum transitions the change in energy ∆ is .

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Physical Chemistry V – reading material only for students at Miranda House, University of Delhi 2021

The figure below gives the frequency for resonance for some other nuclei which have nuclear
spin = ½. The external magnetic field is 2.35 :

http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/nmr/Images/nucfreq1.gif

Population of the energy levels:

The population of the energy levels follows Boltzmann distribution. For a sample at
temperature, T, if is the population of the higher level and is that of the lower
level, then:
∆
= exp( ).

This implies that as long as ≠ 0, the higher level will always have a finite population,
i.e. ≠ 0.

For a sample of 1H at room temperature(~300 ), if = 2.3487T, then ∆ ≅ 7 x 10 .

≅ 1 – (1 x 10-5) ≅ 1.

From this expression it is evident that when resonance occurs, upward and downward
transitions are induced practically to the same extent. However, while the lower energy state is
more populated than the upper, upward transitions predominate slightly and a net absorption
of energy occurs from the incident electromagnetic radiation. This small net absorption leads
to the NMR signal.

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Physical Chemistry V – reading material only for students at Miranda House, University of Delhi 2021

http://www.johnwiley.net.au/highered/chemistry2e/wileyplus/basics/nmr/content/page0001.p
ng

NMR spectrometer – a schematic representation of the instrument is:

https://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/nmr/Images/spctrmtr.gi
f

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Physical Chemistry V – reading material only for students at Miranda House, University of Delhi 2021

Larmor precession (named in honour of Sir Joseph Larmor (1857–1942) an English

mathematician):
The action of the external magnetic field, on the spinning nucleus (or spinning electron) is
to induce a precession of the axis of the spinning particle.
When placed in a magnetic field, charged particles precess about the magnetic field. In NMR,
the charged nucleus, exhibits precessional motion at a characteristic frequency known as the
Larmor precessional frequency.

Spinning Top Analogy:

Often it is difficult in NMR to understand the microscopic processes that are occurring.
However, precession is easily observed on the macroscopic scale, as toy tops. When a top is
spun, it rotates about a central axis (Figure below). The angular momentum of the top (L) is
aligned along this central axis. If the top is set at an angle, the central axis will move in a circle.
The top now spinning along its own central axis precesses around in a circle around the earth’s
gravitational field.

This diagram explains the precession of a top. The torque created by the force of gravity applied
at the centre of gravity and the reactive force applied where the top touches the table causes
the top to precess.
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Ma
ps/Supplemental_Modules_(Physical_and_Theoretical_Chemistry)/Spectroscopy/Magnetic_
Resonance_Spectroscopies/Nuclear_Magnetic_Resonance/NMR_-
_Theory/Larmor_Precession
As mentioned earlier, some atomic nuclei contain intrinsic spin. The nucleus, like a top, will
spin along an axis, which is the direction of the angular momentum for the nucleus. The spin
of the nucleus is related to the magnetic moment of the nucleus.

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Physical Chemistry V – reading material only for students at Miranda House, University of Delhi 2021

https://www.researchgate.net/profile/Kabindra_Kafle/publication/258167196/figure/fig2/AS:
613911678177312@1523379358764/Splitting-of-nucleus-spin-states-m-12-and-12-under-
the-influence-of-the-external.png

https://lh3.googleusercontent.com/proxy/xiDke6QDl1Mo0Cv-FlI9pqZky0-
T2aPnTEDVr9ott8gTAKggwhcXPUZcNXsFxYKEm9YlanrxB5Oll_53bpYcWHFRF5AtId7
xnjH7Zo-p05AGs-udumGxlJcLcwfR

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Physical Chemistry V – reading material only for students at Miranda House, University of Delhi 2021

The interaction of the magnetic moment with the external magnetic field produces a
torque. This torque causes the magnetic moment to precess about the external magnetic field.
The rate of precession, ω is:

µ
= | ⃗|

The Larmor precession frequency, is:

µ
= ={ ⃗
}

{ ( )}
= Hz
{ ( )}ħ

Hence the Larmor precessional frequency has the same magnitude as that corresponding to the
incident electromagnetic radiation frequency. This ‘matching’ of frequencies ensures a
coherent interaction between the nuclear spin in the sample and the incident electromagnetic
radiation.
The Larmor precessional frequency is specific to each nucleus and is dependent on the external
magnetic field that the nucleus experiences.

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Chemical shift:
Till now the bare 1H nucleus has only been considered. However, this situation does not occur
in practice as all nuclei are associated with electrons and a chemical environment. When a
sample is placed in a magnetic field, the electron charge cloud surrounding the nucleus (or
nuclei) will circulate in a direction opposing the external magnetic field. According to Lenz’s
law, the magnitude of this opposing induced magnetic field, is directly proportional
to the external applied magnetic field . Hence:

⍺ .
The extent of screening/shielding of the 1H nucleus from the external applied magnetic field
is understood in terms of the screening constant, σ.

= .

This induced magnetic field opposes the external applied magnetic field so the effective
magnetic field, experienced by the 1H nucleus is:

= − = − = (1 − )

This effective field will vary depending on the local environment /local electron charge cloud
of a particular 1H in the sample. Hence for a sample which has i chemically distinct protons
the magnetic field experienced by each of the i protons will be different. Hence:

= (1 − ), where represents the screening constant for the ith proton.

https://chem.libretexts.org/@api/deki/files/12645/nmr-
3.png?revision=1&size=bestfit&width=652&height=326

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Consider a sample of methanol, CH3OH. Here there are two types of 1H :

 three equivalent methyl protons and

 one hydroxyl proton.
Since the oxygen atom has a higher electronegativity than the carbon atom, the oxygen atom
will tend to ‘pull’ the electron charge cloud associated with the O-H bond towards itself. Hence
the hydroxyl 1H will be more exposed to the magnetic field than the methyl protons. This
implies that the methyl protons will be more shielded/screened from the external magnetic field
or that > . Due to this difference in the screening constants, the magnetic field
‘felt’ by the methyl protons will be different to the magnetic field ‘felt’ by the hydroxyl
protons :

= (1 − ) and = (1 − ).

Since > , hence > .

From the resonance condition, it is clear that the hydroxyl (O-H) 1H will now precess at a
greater frequency as compared to the methyl (C-H) 1H.
If the frequency of the incident electromagnetic radiation is fixed and the external applied
magnetic field is varied/swept, then the hydroxyl (O-H) 1H will satisfy the resonance
condition at a lower external magnetic field while the methyl (C-H) 1H will satisfy the
resonance condition at a higher magnetic field.

Since > , the hydroxyl proton experiences a greater magnetic field and hence
1
the energy levels of this H are more widely spaced apart as compared to the energy levels
associated with the methyl protons. As the magnetic field is swept from left to right (lower
values to higher values), the energy level spacing will constantly increase. Resonance will
occur when the energy level spacing, ∆ ‘matches’ the frequency of the incident
electromagnetic radiation. If the incident electromagnetic radiation is at 100 , the hydroxyl
1
H will resonate at a lower value of the external magnetic field as compared to the methyl
1
H. The area under each NMR peak is directly proportional to the number of equivalent protons.
Hence the intensity of the two peaks will be in the ratio 1: 3.

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(Figure from Fundamentals of Molecular Spectroscopy by Banwell and McCash)

Sweeping the magnetic field from left to right implies the magnitude of the same is
increasing. The value of ∆, the chemical shift difference between the two peaks is observed to
be 3.26µT. This difference could equally well have been observed in terms of changing
frequency had the magnetic field been kept fixed.

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 [DOCUMENT TITLE]
Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021
1
From the resonance condition, it is evident that for a H NMR spectrometer operating at
100MHz:
2.3487 ≡ 100
Hence 3.26 ≡ 139 .
Chemical shift values are defined only in terms of one scale which is referred to as the
δ -scale. This scale is independent of the units. The chemical shift value on this scale is
represented in .
Resonance for the hydroxyl 1H occurs at:
∆ (1 − )
= =
ℎ ℎ ℎ
Resonance for the methyl 1H occurs at:
∆ (1 − )
= =
ℎ ℎ ℎ

Hence the spacing between the two peaks is, ∆ = ( − )

However, the values of the screening/shielding constant, , are dependent only on the
electronic environment and are independent of field and frequency hence so must chemical
shift values.
Chemical shift values are reported as a fraction of either the applied field, or the incident
electromagnetic radiation frequency, .

Therefore, ∆ = = 1.39 x 10 = 1.39

OR
3.26µ
∆= = 1.39 x 10 = 1.39
2.3487
Usually the x-axis of the NMR spectra are ‘swept’ for 10 .
Since: 1.39 ≡ 3.26µ ; hence 10 ≡ 23.4532 µ .
(Note: Actually 10 ≡ 23.4870µ , the difference in the values since the ∆ value above
has been rounded off to 3.26µT)
The magnetic field is swept from (2.3487T – 23.5 µ ) to 2.3487T.
1
10 on this 100 H NMR instrument will be 1000 .

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 [DOCUMENT TITLE]
Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

If the NMR spectrometer is operating at 60 for 1H nucleus, then the external magnetic
field will be 1.41 . If the NMR spectrum for methanol is run on this instrument then the
spacing between the peaks, ∆, will remain 1.39 . This is equivalent to:
∆ x 10
= 1.39
60 x 10
⇒ ∆ = 83.4
1
10 on this 60 H NMR instrument will be 600 .

As the operating frequency increases the separation between the peaks, ∆, increases. Hence
spectrometers operating at higher frequencies (i.e. higher magnetic field strengths) have better
resolution. MRI instruments usually operate at 700 for the 1H nucleus and use
superconducting magnets for the external magnetic field.
Chemical shifts are reported with respect to a reference standard. Theoretically, the bare or
isolated proton which has = 0 would be the ‘best’ reference standard. However, this is
impractical and hence the reference standard used is tetramethylsilane (TMS) (CH3)4Si. The 12
equivalent protons give an intense NMR signal. The value for the protons in TMS is high
and so the NMR signal for these 12 equivalent protons appears at a high magnetic field.

If is the value of the external magnetic field where the reference standard TMS resonates
and the 1H in the sample resonates at then the chemical shift for this 1H in / is:

x 10 OR x 10

Conventionally, in an NMR spectrum, the position of the NMR signal for the reference TMS
is marked at 0 or 0 .
Occasionally, chemical shift values are reported on the τ – scale. On the τ – scale, TMS
resonates at 10 τ. Hence = (10 − ).

TMS is a good reference standard since it is:

 stable,
 low boiling (boiling point 27℃) and hence can be conveniently removed after running
the NMR spectrum,
 chemically inert and hence does not interact with the sample,
 can be easily added to the sample as it is a liquid at room temperature.
The NMR signals for most protons are seen at chemical shift values ranging from 0 to 12 .

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 [DOCUMENT TITLE]
Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

1
H NMR spectrum for methanol at different operating frequencies:

https://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/nmr/Images/methnol1.g
if
When the 1H NMR spectrum for methanol is run at 100 , the peak due to TMS appears at
0 or 2.3487 .
The -CH3 protons resonate at 3.35 i.e. 7.87 to the left of (downfield from) TMS.
The –OH proton resonates at 4.80 i.e.11.27 to the left of (downfield from) TMS i.e.
further downfield from the NMR peak of the -CH3 protons.

At a higher magnetic field/incident electromagnetic radiation frequency:

← ℎ ℎ ,
→

http://chem.ch.huji.ac.il/nmr/software/thermometer.html
The chemical shift values for a particular compound will always be the same immaterial of the
field/frequency of the spectrometer. Spectrometers operating at a higher field/frequency may
show a slightly different value of the chemical shift due to better resolution and accuracy.

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 [DOCUMENT TITLE]
Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

Some typical chemical shift ranges for various functional groups:

-OH

← ℎ ℎ ,

https://lh3.googleusercontent.com/proxy/BFTb7OM48jUs6ZVxXTN9tE4jBORVqh-o-
eE_k2Um-
La2Kc3md1InRcOKlAD0rFdGPELqOWSH1JjobYXe6PNB5WeDqkQGmesEEaJAOox0m2
jtg7Nr0f8LJ2B3RO8iBOIzgoo

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 [DOCUMENT TITLE]
Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

https://www.chemistrysteps.com/nmr-chemical-shift-values-table/

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 [DOCUMENT TITLE]
Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

Some other 1H NMR spectra (low resolution):

https://image.slidesharecdn.com/protonnmrspectroscopypresent-121220044214-
phpapp01/95/proton-nmr-spectroscopy-present-17-638.jpg?cb=1355978687

https://encrypted-
tbn0.gstatic.com/images?q=tbn:ANd9GcT_5W5eT_0F82mrSPPJYOltrid4sdhU3Q8hVQ&us
qp=CAU
The low resolution 1H NMR spectrum of ethanol shows three singlets at :

 methyl proton (CH3) : 1.17

 methylene proton (CH2) : 3.62
 hydroxyl proton (OH) : 5.37

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 [DOCUMENT TITLE]
Physical Chemistry V – reading material for students of Miranda House, University of Delhi 2021

https://www.chemguide.co.uk/analysis/nmr/lnmrmethylprop.GIF
1
H NMR spectrum of acetaldehyde:

https://lh3.googleusercontent.com/proxy/6PrulGKNOcZ1NV9jGmuGaJflMmpzoNbNZrM5G
KePHgz8xuH7evhmbh9RX1ZK_kKQc7310Hz0oBCrinJ-QjrS

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ugBhMNtTnFkaIFM4npi1nXDr4JGzK9qzAGEC3DwC4ZWEWLXiMU

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https://chem.libretexts.org/@api/deki/files/16590/nmrethanoicacid.GIF?revision=1&size=bes
tfit&width=358&height=250

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Chemical shifts are not only explained on the basis of the electron density at a particular 1H
since this not the only factor determining the value of the screening constant, . An important
contribution to the shielding/screening constant arises from the field-induced circulation of
electrons in neighbouring parts of the molecule. This gives rise to small magnetic fields which
in turn effect the magnetic field actually experienced by the 1H.
A few examples:

1. Acetylene (or acetylenic 1H):

The cylindrical charge cloud comprising the triple bond circulates in the presence of an
external magnetic field resulting in a small magnetic field at the 1H which opposes
. The proton is hence shielded and will resonate at a high field/low −value.
The − value lies in the range of 1.5 to 3.5 depending on the specific alkyne.

https://image.slidesharecdn.com/asshumpr-191110064639/95/nmr-diamagnetic-anisotropy-
and-its-effect-on-chemical-shift-11-638.jpg?cb=1573368531
The effect here depends on diamagnetic anisotropy which implies that the shielding and
deshielding depends on the orientation of the molecule with respect to the external applied

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magnetic field. Only a small number of rapidly tumbling molecules are aligned along the
magnetic field but the overall chemical shift is affected by these aligned molecules.

2. Aldehydes (or the aldehydic proton):

The 1H of the –CHO group absorbs at low field/high – value. This value is much
lower than that explained only on the basis of electronegativity.

https://encrypted-
tbn0.gstatic.com/images?q=tbn:ANd9GcTtG3tj9YrhKKv3jz5cBLA2pGd7b6m2eDvfCw
&usqp=CAU
The –C=O group is oriented such that the plane of the trigonal carbon atom is perpendicular to
the external magnetic field. The π – electrons of the aldehydic group circulate such that the
magnetic field induced is along the external magnetic field. The effective magnetic field
experienced by the aldehydic proton is hence enhanced. The aldehydic 1H is hence deshielded
and resonates at low field/high - value.

Chemical shift value for the aldehydic 1H is in the range of 9 to 10 .

For example in CH3CHO the methyl 1H resonates at 2.2 and the aldehydic 1H resonates at
9.72 .

3. Benzene (or aromatic 1H):

Aromatic molecules contain large closed loops of π- electrons in which strong
diamagnetic currents are induced by the presence of the external magnetic field. This
results in the magnetic field experienced by the proton getting enhanced. Hence the
aromatic 1H resonates at low field/high δ-value. This shielding is called paramagnetic
shielding and is due to the ring current effect.
In benzene, the protons resonate at 7.27 . ( Note : the protons in cyclohexane which
does not have any ring current resonate at 1.44 ).

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https://chem.libretexts.org/@api/deki/files/12664/nmr-7.png?revision=1

Generalizations to predict and organize chemical shifts:

The more the number of H-atoms on one C-atom the greater the shielding which implies that
a greater field is applied to obtain resonance, i.e – values decreases in the following:
-CH > - CH2 > - CH3

Electron attraction by adjacent electronegative atoms or groups has a deshielding effect on the
1
H, i.e. the chemical shift is downfield which implies that the -value is high. For example,
the ordering of the chemical shifts is:
F – C – H > – O – C– H > – N – C – H

Unsaturation has a deshielding effect on the chemical shift of the 1H. For example:
Aromatic 1H > 1H in an alkene > 1H in an alkane.

For methyl halides, H3C–X (X being the halogen atom) , the chemical shift for the proton is
explained in terms of electronegativity and is in accordance with the values of
electronegativity: F > Cl > Br > I. The chemical shifts for the methyl proton are 4.26, 3.10,
2.65, 2.16 respectively on the - scale.

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Spin-spin coupling:
1
H NMR spectra where the spin-spin coupling is observed are called high resolution NMR
spectra – HR NMR spectra. Values of the spin-spin coupling constant, J can be evaluated
from the HR-NMR spectra. To ensure a ‘good’ HR-NMR spectrum, the homogeneity of the
external magnetic field is very critical – a homogeneity of ≈ 10 µ is usually required.

Spin-spin coupling and the subsequent changes in the pattern of the NMR signals arises due to
the presence of more than one type of proton in the same sample. For example in methanol
there are two chemically distinct protons. The methyl protons induce a finite appreciable
magnetic field (≥ 10 µ ) at the hydroxyl proton and vice versa. Due to this the ‘actual’
magnetic field ‘felt’ by the hydroxyl proton and the methyl protons changes.
Consider a sample which has two chemically distinct protons – proton A labelled as 1HA and
proton X labelled as 1HX. In general, the proton 1HA can be aligned either parallel to the external
magnetic field or anti-parallel to the external magnetic field . If it is aligned parallel to
then it will induce a magnetic field at 1HX which will oppose the external magnetic field.
However, if 1HA is aligned anti-parallel to then it will induce a magnetic field at 1HX
which will enhance the external magnetic field. Hence 1HX will now experience two distinct
and different magnetic fields: ( – ) and ( + ) with equal probability. Due to these two
different magnetic fields, the 1HX will resonate at two different magnetic fields. This implies
that the singlet NMR peak for 1HX will split into a doublet. The ‘spacing’ between the two
signals of the doublet will be 2 on the Tesla scale. Similarly, the proton 1HX can be aligned
either parallel to the external magnetic field or anti-parallel to the external magnetic field
. If it is aligned parallel to then it will induce a magnetic field at 1HA which will oppose
the external magnetic field. However, if 1HX is aligned anti-parallel to then it will induce a
magnetic field at HX which will enhance the external magnetic field. Hence 1HA will now
1

experience two distinct and different magnetic fields: ( – ) and ( + ) with equal
probability. Due to these two different magnetic fields, the 1HA will resonate at two different
magnetic fields. This implies that the singlet NMR peak for 1HA will also split into a doublet.
The ‘spacing’ between the two signals of the doublet will be 2 on the Tesla scale. The
1 1
interaction between the two spinning protons: HA and HX is called spin-spin coupling. The
magnitude of this interaction is ‘measured’ in terms of the magnitude of the spin-spin coupling
constant, J.

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(Figure from Fundamentals of Molecular Spectroscopy by Banwell and McCash)

(Note: In the figure above the external magnetic field has been designated as .)

In 1H NMR if the two chemically distinct are separated by a ‘distance’ of ≈ 0.1 , then the
extent of the coupling is ≈ 10 . In gases and liquids, due to the rapid movement of the
molecules, the extent of coupling is reduced. In solids/crystals the extent of coupling is

≅ 10 to 10 times that observed in liquids and gases.

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Coupling in liquids can be explained by a simple model. Consider two protons A and X each
having an electron associated with them – electron a and electron x respectively.

(Figure from Fundamentals of Molecular Spectroscopy by Banwell and McCash)

The two protons A and X can be directly bonded as in the hydrogen molecule – if the spin of
proton A is ↑ then the spin associated with electron a will be ↓ this happens as the lowest
energy/most favoured configuration will be when the two magnetic dipoles are parallel i.e.
spins are opposite. Since the electron a has ↓, the spin of electron x must be ↑. Hence the spin
of the proton X will be ↓. Hence the spins of the protons A and X are preferentially paired. From
this model it is evident that:

 immaterial of the distance between the protons A and X there is bound to be some spin-
spin coupling between these two protons,
 the configurations where the nuclear spins of the protons A and X are opposite/anti-
parallel are energetically preferred/lower in energy than the configurations where the
spins are parallel. The difference in energy is small (≈ 10 ) and hence all four
configurations exist.
In the absence of any interaction between the nuclear spins A and X, the lowest energy
configuration will be when both the spins are ↑ - in this situation both the spins are aligned
along the external magnetic field and hence have the lowest energy. The next two levels
will be when the spins are paired, i.e. ↑ ↓ or ↓ ↑ and the energetically highest level will be when
both the spins are ↓.

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When the nuclear spins A and X interact then the ↑ ↑ and ↓ ↓ will be destabilized while the ↑ ↓
and ↓ ↑ will be stabilized. Since the energy associated with the four distinct configurations has
changed, the value of ∆E also changes. This change causes a change in the ‘position’ of the
NMR signals associated with the two different protons A and X.

(Figure from Fundamentals of Molecular Spectroscopy by Banwell and McCash)

Each of the singlets due to the NMR signals for the chemically distinct protons A and X have
been split into doublets intensity ratios 1 ∶ 1 due to the spin-spin interaction.

The equal intensity doublets are seen

 as the four spin states are practically equally likely to exist,

 calculations have shown that the transition probabilities within the selection rule
∆ = ±1 are the same.

The extent of the splitting is measured in terms of the spin-spin coupling constant, J. Since
the magnitude of J is independent of the external magnetic field , the units of J are Hz.

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Sign of the spin-spin coupling constant:
For a simple directly bonded system where A has ↑ and X has ↓ the spin-spin coupling constant,
J is positive. Consider two 1H nuclei each bonded to the same third non-spinning nucleus, e.g.
the CH2 fragment. Labelling the two protons as A and B, this fragment is HA – C – HB :

Nuclei Spin Electron Spin

Proton HA ↑ a ↓
C zero ↑
↑
Proton HB ↑ b ↓

This implies that the spins of the two protons are parallel. By convention the spin-spin coupling
constant for parallel spins is defined as negative. It must be emphasized that this reasoning
cannot be used always and that it is difficult to determine the sign of the coupling constant J
from a spectrum/experiment.
The magnitude of the coupling constant decreases rapidly as the number of bonds between the
two types of protons increases:

Sample/type of system Coupling constant, J/Hz

H2 ≈ 240
H–C-H ≈ 12
H–C–C–H ≈7
H–C–C–C-H ≈ 0.5

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In unsaturated molecules, electrons occupy orbitals which extend over a number of nuclei and
hence are labile. Due to this the coupling constant has a considerable magnitude even for as
the proton spins separated by four bonds.

The rules for spin-spin coupling are:

 Equivalent protons do not split each other. Hence the three methyl protons in a sample
of methanol do not couple with each other.
 Protons that are greater than three bonds away usually do not have any appreciable
coupling.
 Usually one bond coupling >> two bond coupling > three bond coupling.

Coupling between several nuclei:

Different numbers of equivalent adjacent nuclei will cause different splitting patterns, The
splitting pattern can be understood by the ‘family tree’ method. The intensity of the lines and
the pattern of the multiplets formed follows Pascal’s triangle.

https://lh3.googleusercontent.com/proxy/nhAsahzybOlFrqkdWGKIfhLEDt93gnKhDK_MJM
Dryzo4LMUv9eguSiK6S27rV09BP_OYVmnZZn2IJ46a_7ErUIa0weNqQeF30PBrU-yqUYs
If the inner two lines ‘coalesce or merge’ then a triplet pattern is observed – three lines with
intensity ratio 1 ∶ 2 ∶ 1

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https://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/nmr/Images/splitting.gi
f
Example:

In methyl alcohol, the methyl fragment consists of three methyl protons which have the same
chemical shift value since all the three C – H bonds are identical and the shielding at each of
the three protons is the same. Hence the three protons are chemically and magnetically
equivalent. The hydroxyl proton experiences a different magnetic field and hence gives a
different NMR signal. Initially, in the absence of coupling two singlets are observed of intensity
ratio 1 ∶ 3.

When the hydroxyl type proton couples with one proton of methyl group, the singlet of the
hydroxyl proton gets split into a doublet – intensity ratios ∶ which implies 1 ∶ 1 doublet.
Now each leg of the doublet couples with the second X proton – the splitting is ∶
( 1 ∶ 1) and ∶ (or 1 ∶ 1). However the splitting is such that the inner two peaks
coalesce resulting in a pattern of three lines – intensity ratios:
1 1 1
∶ ∶
4 2 4
which is the same as 1 ∶ 2 ∶ 1. This implies the singlet for the hydroxyl proton has been split
into a triplet due to its coupling with the neighbouring two identical protons. Now each leg of
the triplet couples with the third methyl proton – the splitting is ∶ (or ∶ ) and ∶ (or
1 ∶ 1) and ∶ (or ∶ ).

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However the splitting is such that the inner peaks coalesce resulting in a pattern of four lines
– intensity ratios: ∶ ∶ : ( or ∶ ∶ ∶ )

which is the same as 1 ∶ 3 ∶ 3 ∶ 1. This implies the singlet for the hydroxyl proton has been
split into a quartet due to its coupling with the neighbouring three identical methyl protons.
The singlet of the methyl protons couples with the one hydroxyl proton and gets split into a
doublet – intensity ratios ∶ which implies 1 ∶ 1 doublet.

This method is called the family tree method.

The high resolution NMR spectrum for methanol is:

https://i.stack.imgur.com/q0EnR.gif

In ethyl alcohol, the ethyl fragment consists of three methyl protons which have the same
chemical shift value since all the three C – H bonds are identical and the shielding at each of
the three protons is the same. Hence the three protons are chemically and magnetically
equivalent. Similarly the two protons in – CH2 – group are also chemically and magnetically
equivalent but there chemical shift value is different. The ethyl fragment is labelled as A3X2
and has only one value of the coupling constant JAX. Initially, in the absence of coupling two
singlets are observed of intensity ratio 2 ∶ 3.

When the A3 type proton couples with one proton of X2, the singlet of the A proton gets split
into a doublet – intensity ratios ∶ which implies 1 ∶ 1 doublet. Now each leg of the doublet
couples with the second X proton – the splitting is ∶ ∶ and ∶ (or ∶ ).
However the splitting is such that the inner two peaks coalesce resulting in a pattern of three
lines – intensity ratios
3 3 3 1 1
∶ ∶ ∶ 1∶
4 2 4 2 2
which is the same as 1 ∶ 2 ∶ 1. This implies the singlet for the A proton has been split into a
triplet due to its coupling with the neighbouring two identical X protons.

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When the X2 type proton couples with one proton of A3, the singlet of the X proton gets split
into a doublet – intensity ratios 1 ∶ 1. Now each leg of the doublet couples with the second A
proton – the splitting is ∶ and ∶ . However the splitting is such that the inner two peaks
coalesce resulting in a pattern of three lines – intensity ratios ∶ 1 ∶ which is the same as
1 ∶ 2 ∶ 1. Now each leg of this triplet further couples with the third A proton resulting in each
leg being further split into a doublet – the splitting is ∶ ( ∶ ) and ∶ ( 1 : 1) and

∶ ( ∶ ). However the splitting is such that the inner peaks coalesce resulting in a
pattern of four lines – intensity ratios: ∶ ∶ : which is the same as 1 ∶ 3 ∶ 3 ∶ 1.

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This implies the singlet for the X proton has been split into a quartet due to its coupling with
the neighbouring three identical A protons.

(Figure from Fundamentals of Molecular Spectroscopy by Banwell and McCash)

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https://www.researchgate.net/profile/Anastassios_Troganis/publication/242207137/figure/fig
8/AS:668353718927384@1536359352734/
The above is the high resolution 1H NMR (HR-NMR) spectrum of ethanol. The bold letters
denote the protons whose signal is observed. Chemical shift values are in . The spin-spin
1 1
coupling constant for the coupling of the methyl H with the methylene H is ≈ 7

As a comparison, given below is the low resolution NMR spectrum of ethanol as recorded in
the early days of magnetic resonance spectroscopy and the HR NMR spectrum recorded later:

https://unemployedchemist.files.wordpress.com/2014/10/ethanol-nmr.png

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In very high resolution NMR spectra, the splitting of the hydroxyl 1H due to its coupling with
the methylene 1H is also observed. Due to this the singlet of the hydroxyl 1H is split into a
triplet intensity ratio 1 ∶ 2 ∶ 1 and the quartet of the methylene 1H is further split and appears
as a quintet intensity ratio 1 ∶ 4 ∶ 6 ∶ 4 ∶ 1. The quartet of the methylene 1H could also appear
as a series of doublets; i.e. eight lines are observed.

This reasoning is very easily generalized: a group of equivalent nuclei splits a

neighbouring group into ( + ) lines. The intensities of these lines are given by the
line of the Pascal’s triangle.

https://chem.libretexts.org/Courses/University_of_Illinois_Springfield/Introduction_to_Orga
nic_Spectroscopy/5%3A_Proton_Nuclear_Magnetic_Resonance_Spectroscopy_(NMR)/

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The high resolution 1H NMR (HR-NMR) spectra of some compounds are shown below:

https://upload.wikimedia.org/wikipedia/commons/8/80/1H_NMR_Ethyl_Acetate_Coupling_s
hown.png

https://s3-us-west-2.amazonaws.com/courses-images/wp-
content/uploads/sites/1518/2017/10/05154345/image064.png

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Diethyl ether:

https://people.stfx.ca/tsmithpa/Chem361/Labs/spec/GIFs/etherNMR.gif

https://lh3.googleusercontent.com/proxy/g6_BejOvpkajuw3mpTc4b2OaBTs1KSoLd1JslYpF
QKZoOyRceTof2o5IQxZiUI7ou3Eyll6BB5yvUjFWrVJIAWy0SrOCVa4HKdK9F2pAcP-
k88AGMAmk95Z0=s0-d

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Propanoic acid:

https://www.chemguide.co.uk/analysis/nmr/integrator.GIF

Trichloroethane:

https://s3-us-west-2.amazonaws.com/courses-images/wp-
content/uploads/sites/1518/2017/10/05154402/image078.png

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If a given nucleus is spin-coupled to two or more sets of neighbouring nuclei by different J

values, the ( + 1) rule does not predict the entire splitting pattern. Instead, the splitting due
to one J set is added to that expected from the other J sets.

https://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/nmr/Images/splitting.gi
f

https://2.bp.blogspot.com/-
kgnsJr8ciW0/WBCHN64BHqI/AAAAAAAAAaI/iiJuIpmCYDsYASQN09hQXe4KpO5ZKv
xGwCLcB/s1600/26-Oct-16%2B4-02-29%2BPM.jpg

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Magnitude of Some Typical Coupling Constants:

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Line width and intensity of spectral lines
Line width of spectral lines:
An individual atom or molecule is capable of making a transition between energy levels with
well-defined energy as per selection rules. However, real spectral lines are not infinitely
narrow.
Line width of a spectral line is defined as the full width at half the maximum height / maximum
intensity of the spectral line.

The intrinsic or natural line width of a spectral line is due to:

1. Collisional broadening:
The repeated collisions of the molecules in liquid or gas phases cause deformation of
the particles and hence perturb, to some extent, the energy associated with the
molecules/particles. Usually molecular interactions are more severe in liquids than in
gases; hence gas phase spectra usually exhibit sharper lines. Since the number of
collisions depend on pressure and temperature ( ), these factors influence the observed
line width. Usually, the change in line width due to collisions is directly proportional
to the pressure and inversely proportional to √ . In solids the motion or movement of
molecules/particles is limited and less random and hence solid phase spectra are also
observed as sharp lines.

2. Doppler broadening (Doppler shift):

If the velocity associated with the movement of the molecules of the sample is greater
than the velocity of the instrument/spectrometer then broadening occurs. Thermal
motions of radiating particles/molecules along the line of vision “change/alter” the
wavelength / frequency of the incident radiation as “seen/observed” by a stationary
spectrometer/observer. Molecules can move “toward” as well as “away” from the

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observer. Since there is a continuous range of velocities associated with the movement
of the particles/molecules, perfectly monochromatic incident radiation appears to be at
a range of frequencies.

Let the velocity of the “emitter”, here molecules of the sample, be , the frequency of
the incident radiation be and the frequency “observed” by the sample be . Then the
Doppler broadening, referred to as ∆ , is the change in frequency ( − ).
This change in the frequency is equal to where is the velocity of light.

Hence ∆ =( − )=

From the kinetic theory of gases, at a temperature , the approximate velocity

associated with the movement of gas molecules, , is where is the gas constant,
and is the molecular mass of the sample.
Hence, the Doppler shift is:
2
∆ ≈

This implies that the extent of Doppler broadening is directly proportional to √ .

3. Heisenberg’s uncertainty principle:

If a system exists in an energy state for a limited time and the uncertainty in its
energy is , then in accordance with Heisenberg’s uncertainty principle:
ħ
≈ .

Consider the example of line widths in Electronic Spectroscopy. For the electronic
excitations, ≈ 10 . From the above mathematical expression, it then implies that
≈ 10 .
Since =ℎ , ≈ℎ or ≈ ℎ.
Therefore, the uncertainty in frequency, ≈ 10 .
This apparently large uncertainty is small compared to the incident irradiation
frequency usually used in Electronic Spectroscopy. For the incident electromagnetic
radiation which falls in the UV and visible range, the frequency of the incident radiation
is in the range 10 to 10 . The above apparent uncertainty is a small
percentage.

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https://chem.libretexts.org/@api/deki/files/106006/Roberts_and_Caserio_Screenshot_
27-1-1.png?revision=1&size=bestfit&width=560&height=156

For a sharp spectral line the point of maximum intensity can be identified unambiguously.
However, for broad lines the point of maximum can be in doubt. To avoid this the first
derivative can be plotted; the point of maximum in the signal will correspond to the change in
sign of the differential curve. Such differential plots are routinely used in ESR Spectroscopy
where the relaxation times fall in the range.
The figure below shows a typical ESR spectrum for a free radical run when the incident
electromagnetic frequency is of the order of 9 :

https://upload.wikimedia.org/wikipedia/commons/thumb/2/21/EPR_lines.png/300px-
EPR_lines.png

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Since the two factors mentioned above Collisional broadening and Doppler broadening are
both dependent on temperature, the former inversely proportional to √ while the latter directly
proportional to √ , the effects do ‘cancel’ out to some extent. However, temperature does
impact the line width.
Spectra run for the same sample at various temperatures have shown sharper spectral lines at
lower temperatures. Also the extent of broadening will depend on the specific sample and its
molecular mass, .

Intensity of spectral lines:

As has been mentioned and explained earlier the intensity of a spectral line depends on:
1. Transition probability and hence the selection rule.
2. Population of the concerned energy levels
3. Beer-Lambert’s Law