Module 3

The basis of absorption and emission of radiation by molecular

species, the wave properties of the light, the quantum theory of light,
quantum theory of matter, molecular energies and the Born
Oppenheimer approximation, the types of molecular motion and
spectroscopy associated with each.
 Electromagnetic radiation
• Electromagnetic radiation—light—is a form of energy whose behaviour is described by the
properties of both waves and particles
• Some properties of electromagnetic radiation, such as its refraction when it passes from one 
medium to another are explained best by describing light as a wave.
• Other properties, such as absorption and emission, are better described by treating light as a 
particle

Wave nature of light

• Light is energy that travels in a straight line in the form of electromagnetic waves
• When light encounters an object, it may get absorbed, diffracted, reflected, refracted,
scattered or transmitted, depending on the shape and composition of the object, and on the
light’s wavelength
Light can be considered as oscillations of an electromagnetic field – characterized by electric (E)
and magnetic (B) components – perpendicular to the direction of light propagation and to each
other

Electric and magnetic fields of radiation oscillate sinusoidally in mutually perpendicular planes at
right angles to the direction of propagation of radiation
 Wavelength (l)

the distance between two minima or between two maxima is a wavelength

Units: Metre (m), centimetre (cm), millimetre (mm), micrometer (μm), nanometre (nm),
Angstrom (Å); 1 μm = 10−4 cm = 10−3 mm, 1 nm = 10−3 μm, 1 Å = 10−8 cm = 0.1 nm.
• A point P travels with uniform angular velocity  rad s-1 in a circular path of radius A.
• We measure time from instant when P passes O’, =t.
• y= A sin  = A sin t radians
• After a time of 2/  seconds, P will return to O’ completing a cycle.
• /2  = 
• Substituting /2  =  in Eqn y = A sin t, we get
• Considering as a travelling wave,we have distance-time relationship :
x = ct
y = A sin 2t = A sin 2x/c
From c = t and =c/ 
we have : y = A sin 2x/ 

In Spectroscopy, wavelengths are expressed in a variety of units.

• If in the microwave region,  is measured in centimeters or millimetres, while in the infra-red , its micrometres
• In the visible and ultra-violet region, is expressed in Angstrom (A0 ).
Wave Number : The reciprocal of wavelength is called wave number.
Units Number of waves per centimetre (cm−1)

Frequency (n) It is a measure of the number of waves passing through a given point in a unit
time. It is inter linked with wave number through the following equation
 Particulate nature of radiation
Radiation can be also described in terms of particles of energy, called photons
A photon has energy but has neither mass nor charge. Its energy (in Joule) is given as:

where h is Planck’s constant (h =

6.626075 × 10−34 J s).
The above equation relates the
energy of each photon of the
radiation to the electromagnetic
wave characteristics (n and λ).
The internal energies of atoms are small (~10−19 J) because of their small size (~10−10 m).
The individual photon energies are also of the same order and may be more conveniently
expressed in electron volt (eV), a unit equal to the kinetic energy imparted to an electron when
it is accelerated by a potential of 1 V.
The conversion factor between electron volt and Joule is numerically equal to the charge on an
electron.

To appreciate the vast range of photon energies, consider that yellow light (λ ≈ 600 nm) has
a photon energy of ~2 eV, while X-rays from a copper source, with a wavelength of 0.154 nm,
have a photon energy of about 8000 eV.
Electromagnetic Spectrum
 MOLECULAR SPECTROSCOPY AND SPECTRAL REGIONS
The study of electromagnetic radiation with matter in all of its forms, viz., solids,
liquids/solutions and gases is called spectroscopy. Depending upon the energy of radiations but
not the intensity which is a measure of the amount of radiations, spectroscopy has been classifi
ed into different branches
 Hydrogen spectrum (line spectrum)

It’s a line spectrum coming from the quantised energy levels of the H atom
 Molecular spectrum
It’s a band spectrum because it not only involves electronic energy levels but also vibrational
and rotational levels
Rotational and vibrational energies are much smaller than the electronic energies, and so
electronic transitions are accompanied by vibrational transitions (fine structure) and rotational
transitions (hyperfine structure)
Besides translational energy, molecules have three kinds of energies. Changes in these
energies follow the order

since the three are approximately of the order 1-10 cm-1 , 1000 cm-1 and 25000 cm-1 ,
respectively. Hence, each electronic level has its own set of vibrational levels, and each
vibrational level has its set of rotational energy levels
• As a result, each electronic transition is accompanied by simultaneous vibrational and
rotational energy changes, and electronic spectra are broad.
• Electronic transitions produce ultraviolet and visible lines, vibration-rotation transitions
produce infrared lines and pure rotational transitions produce microwave lines.
 The Born–Oppenheimer approximation
• Just as for an atom, the hamiltonian H for a diatomic or polyatomic molecule is the sum of
the kinetic energy T, or its quantum mechanical equivalent, and the potential energy V.
• In a molecule the kinetic energy T consists of contributions T e and Tn from the motions of the
electrons and nuclei, respectively.
• The potential energy comprises two terms, Vee and Vnn, due to coulombic repulsions
between the electrons and between the nuclei, respectively, and a third term V en, due to
attractive forces between the electrons and nuclei.

For fixed nuclei Tn = 0, and Vnn is constant, and there is a set of electronic wave functions e
which satisfy the Schrodinger equation
Hee= Ee e

Where He = Te + Ven + Vee

Since He depends on nuclear coordinates, because of the Ven term, so do e and Ee but, in
the Born–Oppenheimer approximation, it is assumed that vibrating nuclei move so slowly
compared with electrons that e and Ee involve the nuclear coordinates as parameters only

Since the different kinds of energies span different time scales, they can be treated
independently of each other.
This implies that the total Hamiltonian can be written as a sum of Hamiltonians

(1)

and the total wave function can be written as a product of the different wave functions

(2) and (3)

 Inserting equations (1) and (2) into (3) and separation of variables, we get

This is essentially the Born-Oppenheimer approximation, which states that the time frame of
these kinds of motions is so different that they may be considered independent of each other.
Changes in one kind of energy does not affect the other kind of motion

The Hamiltonian for the translational energy is simply the particle-in-a-box Hamiltonian

Solution of this equation leads to the allowed energy levels

The separation between adjacent energy levels is

where M is the mass of the molecule and L the length of the container.
Since both are large and in the denominator, the separations are extremely small and
translational energy levels may be considered continuous and no translational spectroscopy
can be observed

The classification of molecular transitions leads

naturally to a division of spectroscopy
experiments into three groups:
• Electronic spectroscopy (Visible, UV)
• Vibration-rotation spectroscopy (Infrared)
• Pure rotational spectroscopy (Microwave)
 Intensities of Transitions
• When radiation falls on an atom or molecule, the oscillating electric field of the radiation
interacts with the electrons, and in some cases causes a transition from a lower energy state
to a higher one, causing absorption of radiation, or from a higher to lower energy level,
causing emission of radiation.
• The intensity of a transition from one quantum state to another resulting from the
interaction of electromagnetic radiation with a molecule is dependent on matching the
energy of the radiation with differences in the molecular energy levels (ΔE = h).
• It is also dependent on the number of molecules populating the initial state in the transition.
 Boltzmann Distribution Law
In general, the Boltzmann distribution tells us that the ratio of populations varies exponentially
with the energy difference,
=

For 1 mole, the eqn becomes

R=NA KB = 8.314 J K-1 mol-1 , and RT = 298.15×8.314 = 24789 J mol-1

0r RT = 2.48 kJ mol-1
 Electronic level population
For an electronic level difference ΔE is quite high.
If we take a hydrogen atom in the gas phase, ΔE = 1000 kJ mol-1 .
The population of the 2s excited state N2s relative to ground state, N1s is

we can be very confident that there are no 2s hydrogen atoms around at room temperature
Vibrational level population

Next we consider vibrational modes. If we take CO molecules, the vibrational quantum levels
have an energy separation of around ΔE = 25 kJ mol-1 .
Vibrational energy levels (v = 1, 2, 3…) are much more closely spaced than electronic ones.
Hence

If we have a system containing 20000 molecules, then

Nv= 20000 . 5. 10-5 = 1
It means that one out of every 20000 molecules is found at the first vibration excited state
in a time average.
 Rotational level populations
Rotational levels are much more closely spaced than vibrational levels.
For CO the rotational energy levels are around 0.05 kJ mol-1 apart. We can write

The factor of 3 in the equation above arises because the first excited level J = 1 is actually
threefold degenerate (i.e. there are 3 levels all with the same energy). T
his degeneracy factor must be taken into account when assessing the probability of finding a
molecule in a given level
Thus, at room temperature, there are practically no molecules in electronic excited states, few
molecules in excited vibrational states and a sizeable population in excited rotational states.
 Results form Quantum Mechanics

The Rigid Rotator

Let us consider a rotating dumb-bell shaped object which could be a diatomic molecule rotating
about its centre of mass.
The total distance between the two atoms is fixed at its bond length R (r1 + r2).
According to the law of moments

The moment of inertia is given by

Substituting for r1 and r2, we get

where µ is the reduced mass of the molecule

The kinetic energy of a rotating classical object is related to its angular velocity (ω) by (½)Iω 2 .
Since the angular momentum L of a rotating classical object is given by L = Iω, its kinetic energy
can be expressed as

Quantization of Rotational Energies

So far, we considered a classical rotating object. When this object is of molecular dimensions,
quantisation of the energy comes into the picture

The rotational Hamiltonian maybe expressed as

The hydrogen atom wave functions were found to be eigenfunctions of the angular
momentum square operator

It is also found that one of the components is also quantized

Exactly the same kind of solutions exist for the rigid rotator; the only difference is that the
quantum number J replaces l.
Like l, the rotational quantum number J can take on all positive integer values, including zero,
and each J has 2J+1 values of MJ associated with it.
The allowed values of MJ are 0, ±1, …±J, but all these values are degenerate in the absence of
an external field.
The quantity ħ/2I is called the rotational constant and is given the symbol B.
In SI units, it is expressed in Joules (since ! is in J s and I in kg m 2 ).
The restriction of J to integral values means that the rotational energy is quantized.
The lowest energy is zero (when J is zero) and in this state the molecule does not rotate at all.

Allowed energy levels for a diatomic molecule

The rotational energy can be expressed in wavenumber units as

where Ḃ is the rotational constant expressed in wavenumber units (cm -1).

This quantity is equal to B/hc and its value ranges from 1 – 10 cm -1 .
 Quantum Mechanical Harmonic Oscillator

The classical treatment shows that the frequency of vibration is related to the force constant of
the bond and masses of the atoms involved.
The kinetic energy term for the Hamiltonian is

The general relation between force and potential energy in a conservative system in one
dimension is
=-kx
From which we get

The potential energy curve therefore resembles a parabola

Detailed solution of the Schrödinger equation shows that
the vibrational energies are quantized and expressed as

k is the force constant of the bond

and μ is the reduced mass.

The wavenumber is given by

Conversion of the energy expression to reciprocal centimetre units yields

The lowest vibrational energy G(0) is hence given by

or

This is known as the zero-point energy.