Electromagnetic

UNIT 1 ELECTROMAGNETIC RADIATION Radiation

Structure
1.1 Introduction
Objectives
1.2 What is Electromagnetic Radiation?
Wave Mechanical Model of Electromagnetic Radiation
Quantum Model of Electromagnetic Radiation
1.3 Consequences of Wave Nature of Electromagnetic Radiation
Interference
Diffraction
Transmission
Refraction
Reflection
Scattering
Polarisation
1.4 Interaction of EM Radiation with Matter
Absorption
Emission
Raman Scattering
1.5 Summary
1.6 Terminal Questions
1.7 Answers

1.1 INTRODUCTION
You would surely have seen a beautiful rainbow showing seven different colours
during the rainy season. You know that this colourful spectrum is due to the separation
or dispersion of the white light into its constituent parts by the rain drops. The rainbow
spectrum is just a minute part of a much larger continuum of the radiations that come
from the sun. These are called electromagnetic radiations and the continuum of the
electromagnetic radiations is called the electromagnetic spectrum. In the first unit of
this course you would learn about the electromagnetic radiation in terms of its nature,
characteristics and properties. Spectroscopy is the study of interaction of
electromagnetic radiation with matter. We would discuss the ways in which different
types of electromagnetic radiation interact with matter and also the types of spectra
that result as a consequence of the interaction.

In the next unit you would learn about ultraviolet-visible spectroscopy ‒ a

consequence of interaction of electromagnetic radiation in the ultraviolet-visible range
with the molecules constituting the matter.

Objectives
After studying this unit, you should be able to:

• describe the wave nature of electromagnetic radiation,

• define the parameters that characterise wave form of electromagnetic radiation,
• outline and explain the properties of the electromagnetic radiation that arise due
to its wave nature,
• describe the quantised or particle nature of electromagnetic radiation,
• explain the phenomena of absorption, emission and scattering of
electromagnetic radiation, and
• explain the origin of line spectrum and band spectrum.

7
Molecular Spectroscopic
Methods-I 1.2 WHAT IS ELECTROMAGNETIC RADIATION?
You feel hot while sitting close to a fire. You would say it is obvious, what is so
special about it? Fine! But have you ever wondered what makes you feel hot or in
other words how does the energy as heat reaches you from the source? This is in the
form of electromagnetic (EM) radiation. Heat energy reaches us in the form of infra-
red radiations which is a type of electromagnetic radiation. Let us learn about EM
radiation in general.

An electromagnetic radiation may be defined as the radiant energy which is

transmitted through space at enormous velocities. It exists in various forms; the visible
light and radiant heat being the easily recognised forms which we experience in
daytoday life too. The EM radiation, unlike sound, does not require a medium for
transmission and pass readily through vacuum and in vacuum, the velocity of radiation
is 3 × 108 m s . The study of different ways in which EM radiation can interact with
‒1

matter is of great importance in Chemistry. In order to understand these interactions it

is therefore necessary to have knowledge of the properties of EM radiation. The
properties of an electromagnetic radiation could be explained in terms of both classical
wave model (wave mechanics) and particle model (quantum mechanics). Let us learn
about these models of EM radiation and the properties associated with them.

1.2.1 Wave Mechanical Model of Electromagnetic Radiation

In the wave mechanical model, the electromagnetic radiation is considered to be
sinusoidal in nature, i.e., varying like a sine function. According to the Maxwell’s
theory, an electromagnetic wave can be visualised as oscillatory electric and magnetic
fields travelling in the planes perpendicular to each other and also to the direction of
propagation (Fig. 1.1). This gives rise to its name viz., electromagnetic radiation.
However, since it is the electrical effect that is responsible for the phenomenon of
interest to a chemist, it is generally represented in terms of the electric field only.

Fig. 1.1: An EM radiation showing oscillatory electric and magnetic fields

Characteristic Parameters of Electromagnetic Radiation

The electromagnetic wave is characterised in terms of a number of parameters. These

are as follows:

8
Amplitude: It refers to the maximum height to which the wave oscillates and equals Electromagnetic
the height of the crests or depths of the troughs. It is a measure of the radiant power of Radiation
the radiation. The radiant power refers to the energy of the radiation striking at a
given area per unit time. It is denoted as P and is related to the square of the
amplitude. It is important to remember that the radiant power is not related to the
wavelength. A closely related term is called intensity of the radiation which is
denoted as I and is defined as the radiant power per unit solid angle.

Wavelength: It is the linear distance between two consecutive wave-crests or wave-

1 cm = 10-2 m
troughs or the distance of complete cycle as shown in Fig. 1.1. It is represented by a
1 µm = 10-6 m
Greek letter lambda (λ) and expressed in terms of metre (m), centimetre (cm), 1 nm = 10-9 m
micrometre (µm), nanometre (nm) or Angstrom (Å) units. The wavelength of 1 Å = 10-10 m
electromagnetic radiation varies from a few Angstroms to several metres.

Frequency: It is defined as the number of wave crests or wave troughs that pass
through a given point per second. It is represented by a Greek letter nu (ν) and Different spectroscopic
techniques use different
expressed in terms of second inverse or per second (s −1 ) or Hertz (Hz). The units for wavelength.
relationship between wavelength and frequency is given as: Nanometre is popular for
c UV-visible regions while
ν= micrometre (µm) is
λ preferred for the IR
Where, the wavelength λ is in metres, the frequency ν is in reciprocal seconds (s −1 ) region.
and the velocity of light, c = 3 × l08 m s −1 .

Wave number: It equals the number of waves per centimetre or per unit distance. It
is denoted as nu bar (ν ) and is equal to the reciprocal of the wavelength expressed in
metres (m). The unit of ν is metre inverse (m −1 ) though cm‒1 is also commonly
employed; where the wavelength is expressed in the units of cm.
1
ν =
λ
Velocity: It is defined as the linear distance travelled by the wave in one second. The
velocity in metres per second can be obtained by multiplying frequency in second
inverse by wavelength in metres.

c = ν (s −1 ) λ

The velocity of EM radiation depends on the medium. It has maximum value in

vacuum and equals 3.00 × 108 m s −1 .

Energy: The energy of the electromagnetic radiation depends on its wavelength or

frequency. The relationship is as under.

hc
E = hν = ... (1.1)
λ

where, h is the Planck’s constant and has a value of = 6.626 × 10 −34 J s, ν is the
frequency c is the velocity and λ is the wavelength. As you can probably make out
that the energy is directly related to the frequency and inversely related to the
wavelength of the radiation. In other words a high frequency radiation will have a
higher energy while a longer wavelength radiation will be low in energy. Table 1.1
summarises the important characteristics of the EM radiation, their relationship with
wavelength and the common units of their measurement.

9
Molecular Spectroscopic Table 1.1: Characteristics of EM radiation, their relationship with wavelength and
Methods-I common units of measurement

Characteristic of Relationship with

Common Units
EM Radiation Wavelength

Wavelength λ m, µm, nm

1
Wave number ν = m -1, cm -1
λ
c
Frequency ν= s -1 (Hz)
λ
Velocity c = νλ m s -1

hc
Energy E= Joule (J)
λ

The Electromagnetic Spectrum

Depending on the wavelengths, electromagnetic radiation is of many types and
Deuterium lamp is constitutes what is called an electromagnetic spectrum (Fig. 1.2). The EM spectrum
commonly employed as is divided into different regions on the basis of the methods required to generate and
the source of UV detect them. The radiations of different regions differ in terms of their characteristics
radiations.
like energy, wavelength, etc. The electromagnetic spectrum is divided into γ-rays,
x-rays, ultraviolet, visible, infrared, microwave and radio waves, etc. in terms of
increasing wavelengths.

Fig.1.2: Electromagnetic spectrum showing different regions

The visible region of the spectrum which the human eye can sense is very tiny, as
compared to the other spectral regions. Since the range of electromagnetic spectrum is
quite large, it is expressed in logarithmic or exponential scale.

The sources of radiation mostly give EM radiation spread over a range. In other words
the EM radiation emitted by the source contains a number of radiations having slightly
different wavelengths. For example, a hot deuterium lamp emits radiations in the
wavelength range of approximately 190-380 nm. Such a radiation is called

10
polychromatic radiation signifying that it consists of many radiations of different Electromagnetic
wavelengths. We can generate or separate out radiation of a single wavelength from Radiation
the polychromatic radiation by using a suitable device called monochromator. Such a
radiation is called a monochromatic radiation i.e., consisting of a single wavelength.
You would learn about monochromators in the next unit.

Before going ahead, try to answer the following SAQ.

SAQ 1
How is an electromagnetic radiation different from sound waves?
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1.2.2 Quantum Model of Electromagnetic Radiation

The wave model of electromagnetic radiation described above was successful in
explaining a number of observed phenomena however, it fails to account for the Max Planck proposed the
absorption, emission and scattering of radiant energy, discussed in Sec 1.3 and 1.4. It concept of quantisation to
is so because when an electromagnetic radiation is absorbed or emitted, there is a explain the experimental
permanent transfer of energy which goes against the very concept of wave nature of observations in case of a
black body and Einstein
energy. Therefore a new model for the electromagnetic radiation was required. This is
used this concept to
called the quantum model. The quantum model (also called particle model) of explain photoelectric
radiation was necessitated by the experimental observations in case of black body effect.
radiation and the photoelectric effect. Let us briefly recall these.

Black Body Radiation

You have learnt earlier that all heated objects emit electromagnetic radiation and the
wavelengths of these radiations depend on the temperature of the object. For example,
at relatively low temperatures, a metal rod emits infrared radiation which we cannot
see but feel as heat. As the temperature is raised to about 600°C a dull red colour is
visible and at about 2000 °C it glows white. One can visit a blacksmith and observe
the changes in the glow of iron as it is heated to higher and higher temperatures.

However, the energy radiated by a hot surface depends on its nature and surface area,
besides the temperature. For a given area and temperature, a black surface radiates
more energy per second than a polished surface. At a given temperature the maximum
radiation would be given out by a perfectly black surface. The experimentaly observed
data on radiant intensity emitted at different wavelengths by a perfect black surface
(called black body) at different temperatures could not be explained by classical
mechanical principles. This required a relook at the nature of the radiation.

Photoelectric Effect
In 1887, Hertz observed that when a light of appropriate wavelength falls on a clean
surface of metal plate placed in an evacuated vessel a stream of electrons is emitted.
These electrons are called as photoelectrons because these are emitted due to light.
As moving electrons constitute electricity, the phenomenon of emission of
photoelectrons is referred to as the photoelectric effect. Alkali metals with loosely
held electrons are better photoelectric metals. Like blackbody radiation, the existence
of the photoelectric effect and the related experimental observations could also not be

11
Molecular Spectroscopic explained by classical physics. These and some other experimental phenomenon
Methods-I
could be explained in terms of the quantum mechanical model. Let us learn about it.
In the quantum or particle model, the radiant energy is considered as stream of
discrete particles or packets of energy called as quanta (singular, quantum) whose
energy is proportional to its frequency. The two are related as,
The quantum of light was
E = hν
later called a photon. Alternatively, the energy of the quantum can be related to the wavelength or wave
number as follows
c
E=h or E = hcν
λ
It is important to remember that energy of the photon is not same as the radiant
power. The radiant power includes the energy of the photon as well as the number of
the photons in the radiation.

Let us take an example to understand the application of the relationship between the
energy and other characteristics of the radiation.

Example 1: A microwave radiation has a frequency of 12 gigahertz.

a) What would be the energy of the photon corresponding to this radiation?
b) Calculate the wavelength of the radiation.
(h = 6.626 × 10 –34 J s and 1 gigahertz = 109 Hz)

Solution:
The energy of radiation is related to the frequency as, E = hν

Substituting the values of frequency and Planck’s constant, we get

E = 6.626 × 10−34 Js ×1.2 ×1010 s −1 = 7.95 ×10 −24 J

∴The energy of the photon having a frequency of 12 gigahertz = 7.95 × 10 −24 J

c
Further, since E = h we can rearrange the equation to get
λ
E
λ=
hc
Substituting the values of E, h and c we get

7.95 × 10 −24 J
λ= = 400 nm
6.626 × 10 −34 J s × 3.0 × 10 8 m s −1

∴The wavelength of the radiation = 400 nm

Try to answer the following SAQ to assess your understanding about the
characteristics of the electromagnetic radiation.

SAQ 2
The green light has a wavelength of 535 nm. Calculate the energy of a photon of green
light.
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12
 Electromagnetic
1.3 CONSEQUENCES OF WAVE NATURE OF Radiation
ELECTROMAGNETIC RADIATION
The wave nature of electromagnetic radiation is manifested in terms of a number of
important phenomena. These are interference, diffraction, dispersion, refraction,
reflection, scattering, and polarisation etc. Let us learn about these in the following
subsections.

1.3.1 Interference
In 1803, an English physicist Thomas Young reported the results of his famous double
slit experiment on light. He observed that when a monochromatic light was made to
pass through two closely spaced narrow slits and to fall on a distant screen a series of
dark and light bands (called fringes) were observed on the screen (Fig. 1.3).

The beautiful coloured

patterns observed in the
Peacock feathers and in
the compact disc are due
to interference of light.
Fig. 1.3: A monochromatic light showing dark and light bands when passed
through two closely spaced narrow slits
The origin of these fringes was explained in terms of the interference of the wavelets
originating from the two slits. The bright spots were attributed to the constructive
interference of the wavelets, meaning thereby that the wavelets are in phase and when
they interfere, their amplitudes add up to give the bright spot. On the other hand, when
the wavelets are not in phase they undergo destructive interference whereby these
cancel each other’s amplitudes and result into a dark spot. The third possibility is that
the waves are partially in phase and partially out of phase. In such a situation the
resultant amplitude is the sum of the amplitudes of the two wavelets at different times
or distance (Fig. 1.4).

Fig. 1.4: Schematic representation of interference of waves

13
Molecular Spectroscopic 1.3.2 Diffraction
Methods-I
You might have experienced the formation of waves in a pond of still water when
Diffraction was first disturbed by throwing a stone. Have you ever seen the changes in such a wave when it
observed by Francesco encounters a small barrier or a narrow opening? If you have observed, you would
Grimaldi in 1665. He recall that these waves bend or change their direction of propagation on meeting a
noticed that light waves barrier or an opening. This phenomenon of bending of a wave round the corners of
spread out when they pass
through a slit.
sharp barriers or through narrow openings is called diffraction. Electromagnetic
radiations also show this phenomenon. The consequence of diffraction can be
observed by placing a photographic plate in the path of diffracted radiation. The
occurrence of a pattern of alternate bright and dark bands is characteristic of the
diffraction (Fig.1.5). The intensity is maximum at the central band and decreases
gradually as the distance increase and not visible beyond certain distance. The
presence of light in the areas that are otherwise expected to be dark accounts for the
bending of light.

Diffraction is a wave
property, which can be
observed not only for
electromagnetic
radiations, but also for
mechanical and acoustical
(i.e., related to sound)
waves.

Fig. 1.5: Diffraction of monochromatic radiation through a narrow slit and the resulting
intensity pattern

The diffraction phenomenon is a consequence of interference of wavelets originating

from different parts of the slit. The inner corners as well as the central part of the slit
act as the sources of new wavelets which interfere to give the observed intensity
patterns.

The extent of diffraction through narrow openings (slits) depends inversely on the
width of the slit i.e., narrower the slit greater the diffraction. The effect becomes
observable when the size of the slit is comparable to the wavelength of the light.

1.3.3 Transmission
When radiation passes through a transparent medium, its velocity is found to be
reduced as compared to that in the vacuum. This is due to the interaction of radiation
with the constituents of matter. The extent of reduction in velocity depends on the
nature and concentration of atoms, ions or molecules present in the medium. When
the radiation interacts with the atoms and molecules present in the medium, it results
Polarisation is a in their periodic polarisation i.e., the deformation of their electron clouds. In the
phenomenon of absence of any absorption, the energy required for polarisation is retained only
temporary deformation of
electron clouds associated momentarily ( 10 −14 − 10 −15 s) and reemitted without any alteration and the substance
with atoms and molecules returns to its original state. Since the re emission of the radiation is delayed for some
time; i.e. the radiation takes a little longer to travel through a distance, its velocity
decreases. However, since there is no absorption of the radiation, the frequency of the
radiation does not change. Thus the transmission of radiation involves a series of
polarisation processes wherein the atoms, ions and molecules act as intermediates.

The extent of interaction of the radiation with matter can be expressed in terms of an
important parameter called the refractive index of the medium. It is defined by the
following equation:

14
 c Electromagnetic
ηi = Radiation
νi
where, ηi is the refractive index for the radiation of a given frequency i, and c and
The type of dispersion
ν i are the velocities of the radiation in vacuum and in the medium, respectively. The plays important role in
variation of refractive index of a substance with wavelength of the radiation is called the selection of optical
as dispersion. If the refractive index increases gradually with increasing frequency, it components for
is called a normal dispersion, and if there is a sharp change in refractive index it is instruments.
termed as an anomalous dispersion.

1.3.4 Refraction
When a beam of light travelling through air falls on glass at an angle, it abruptly
changes its direction or in simple words, it bends. A similar effect is observed when
the light emerges back into air after passing through the glass. In general, when a
radiation falls on the interface of two transparent media of different densities, it
abruptly changes its direction. This is called refraction of the radiation. Refraction is
a consequence of the difference in the velocity of radiation in the two media. When
the radiation passes from a rarer medium (say air) to a denser medium (say glass) it
bends towards the normal to the interface. If the order of the media is reversed then it
bends away from the normal to the interface at the point of incidence. The process of
refraction in case of radiation passing from rarer to a denser medium can be depicted
diagrammatically as shown in Fig. 1.6.

Bending of pencil in a
glass of water is a
consequence of
refraction.

Fig. 1.6: Phenomenon of refraction of radiation

According to Snell’s law:
sin θ 1 η 2 v1
= =
sin θ 2 η1 v 2
where, θ1 and θ2, are the angle of incidence between the incident ray and the normal
and the angle of refraction between the refracted ray and the normal, respectively. η1
and η 2 are the refractive indices of the medium that the light is entering into and
leaving (or entering from) respectively; v1 and v2 correspond to the velocities of light
in medium 1 and 2, respectively.

1.3.5 Reflection
The fact that the angle
When a radiation travelling in a medium is incident on a medium of different
of incidence is equal to
refractive index, a fraction of the radiation bounces back at an angle equal to the angle the angle of reflection
of incidence of the radiation. This is called reflection of light. Larger the difference in is sometimes called the
refractive index the greater is the fraction of reflected radiation. The fraction of the "law of reflection".

15
Molecular Spectroscopic reflected light is given as below:
Methods-I
Pr (η 2 − η1 ) 2
=
Po (η 2 + η1 )2

where P0 and Pr are the radiant powers of the incident and reflected beams,
respectively; η1 and η 2 are the refractive indices of the two media. Fig. 1.7 shows the
reflection and the refraction of radiation.

Fig.1.7: Diagrammatical representation of reflection and refraction

SAQ 3
What do you understand by the diffraction of radiation? How is it related to the slit
width?
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1.3.6 Scattering
As we have seen earlier (subsection 1.3.3), interaction of radiation with matter, cause a
momentary retention of radiant energy by atoms, ions or molecules due to their
polarisation. If the polarised particles are small, destructive interference of the
re-emitted radiations eliminates the remitted radiations in all the directions other than
original path of the light. What we observe is the radiation transmitted in unaltered
direction. Keen experimental observations, however, revealed that a minute fraction
of the radiation is transmitted in all directions. This phenomenon is called scattering
and the radiation is referred to as scattered radiation. The intensity of the scattered
radiation depends on the size of the particles constituting the medium.

1.3.7 Polarisation
Ordinary radiation is created by vibration of electric charges in all possible directions.
Light emitted by the sun, Thus a radiation consists of a bundle of electromagnetic waves in which the vibrations
or a lamp or by a candle are equally distributed among an infinite series of planes perpendicular to the direction
flame is unpolarised in
of propagation. Such a radiation which is vibrating in more than one plane is referred
nature.
to as unpolarised radiation. If we observe an approaching unpolarised radiation from
the direction opposite to its direction of propagation we would observe a set of infinite
electrical vectors that oscillate around a fixed point as shown in Fig. 1.8.

16
 Electromagnetic
Radiation

Fig.1.8: An unpolarised radiation passing through a polariser to give a plane polarised

light
When such an unpolarised light is passed through a polariser, it cuts off all the
radiations oscillating in different planes; and allows only those rays that vibrate in any Polarised light waves are
one particular plane to pass through. The emerging radiation is called as the plane light waves in which the
polarised light. The electric and magnetic components of the plane polarized light vibrations occur in a
vibrate at right angles to each other as shown in Fig.1.1. The process of transforming single plane.
unpolarised light into polarised light is known as polarisation. Calcite or quartz
crystals are commonly used to obtain the polarised radiations.

As mentioned earlier, spectroscopy is a study of interaction of radiation with matter

and the consequences there of. Before formally getting into spectroscopy which we
will discuss in the next unit, it is worthwhile to understand different possibilities that
exist for this kind of interaction. Before studying further you can try answering the
following question.

SAQ 4
What is plane polarised light? How is it obtained?
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1.4 INTERACTION OF EM RADIATION WITH MATTER

In order to understand the nature and mechanism of interaction of radiation with
matter we would first like you to recall what you have learnt about nature of matter in
earlier classes. You would recall from your understanding of the quantum mechanical
description of the electronic structures of atoms and molecules constituting matter,
that these have unique set of quantised electronic energy states available to them.
These arise from the motion of electrons around the nucleus and the electrons in atoms
and molecules are present in the allowed or permissible energy states only.
However in case of molecules, the rotation and vibration motions are also quantised in
addition to these electronic energy states. The allowed energy level with the least
energy is termed as the ground state while the rest are called excited states. The
energy levels for a molecule can be schematically shown as given in Fig. 1.9.

17
Molecular Spectroscopic
Methods-I

There are a number of

vibrational energy levels in
an electronic state and a
large number of rotational
energy levels are there in a
vibrational energy level.

Fig. 1.9: Schematic diagram showing energy levels for a molecule

The transitions amongst these energy states may be brought about by absorption of a
photon of suitable energy or these may lead to release of such a photon. In simple
words we can say that the system may absorb energy and go from the lower energy
state (ground state), E1, to higher energy state (excited state), E2 by absorbing a photon
of energy equal to the difference of the energies of the two states i.e.,

∆E = E2 – E1 = hν

where, h is the Planck’s constant and has the value of 6.626 × 10−34 J s (joules
second) ν is the frequency of electromagnetic radiation which is causing the energy
changes. Alternatively, a system initially in the higher energy state E2 can go to the
lower energy state E1 by emitting a photon of the energy equal to the difference in
energies. The energy changes can be shown as in Fig. 1.10. As you can see here in ∆E
is the energy change associated with the transition between the energy levels E1 and
E 2.

E2

E1

Fig. 1.10: Diagram showing energy change during transition between energy levels
Yet another possibility is of the radiation getting scattered. The three phenomena
occurring due to interaction of radiation with matter viz. absorption, emission and
scattering are explained in the following subsections.

1.4.1 Absorption
At a given temperature different species (atoms and molecules) are distributed
amongst the allowed energy levels in accordance with the Boltzmann distribution.
According to the Boltzmann statistical distribution, the population of the ground state

18
i.e., the number of species in the ground state is highest and it keeps on decreasing as Electromagnetic
we go to higher energy levels. The population of any excited state relative to that of Radiation
the ground state is given by the following formula.

∆E
Ni −
= e kT
N0

where Ni and N0 are the populations of the ith level and the ground state respectively;
∆E is the difference in the energies of the ground and excited state, k is called the
Boltzmann constant and T is the absolute temperature. Let us calculate the population
of an energy level, having energy of 2 kJ mol-1 relative to the energy at ground state at
300 K.
2 × 10 3 J mol −1
∆E = E f − E i = 23 −1
= 3.32 × 10−21 J
6.022 × 10 mol

∆E 3.32×10 −21 J
Ni − −
= e kT = e 1.38×10 JK ×300 K = e−0.802 = 0.4484
− 23 −1

N0

This implies that for every 10000 species at the ground state there are 4484 species at
the level that has energy of 2 kJ mol-1 relative to it.

Let us see what happens when a polychromatic radiation is made to impinge upon a Boltzmann constant is gas
sample containing atoms or molecules. One simple possibility is that it gets constant per molecule and
transmitted unaffected through the sample. The other possibility is the radiation can be obtained by dividing
coming out of the sample is devoid of the certain frequencies. In the latter case the the gas constant with the
missing frequencies are said to be absorbed by the sample. Only those photons are Avagadro’s number;
absorbed whose energy matches with the difference in energy of any two energy states k = R/NA; its value is
of the sample provided the transition amongst these levels is allowed. Fig. 1.11 (a) 1.38 × 10−23 J K−1.
shows that the polychromatic radiation from a source when dispersed with a prism or
any suitable device, it gives a continuous spectrum of EM radiation. When the
radiation is passed through a sample before being dispersed as in Fig. 1.11 (b), certain
frequencies are found to be missing. These are absorbed by the sample. The spectrum
so obtained is called an absorption spectrum.
Whether a transition is
allowed or not, is
governed by certain rules
called selection rules

Fig. 1.11 (a): Dispersion of a polychromatic radiation through a prism to give a

continuous spectrum

19
Molecular Spectroscopic
Methods-I

Fig. 1.11 (b): Schematic representation of the set up for getting an absorption
spectrum
As the difference in the energy levels is unique for each species, knowledge of the
frequencies absorbed by a given species may provide information about the species
being studied. The absorption characteristics of a given species are described in terms
of the absorption spectrum, which is a plot of the extent of absorption by the species as
a function of wavelength or frequency or wave number of the radiation absorbed. The
nature of spectrum obtained depends on the nature of the absorbing species. Let us
take up the absorption of radiation by atomic and molecular species.

Atomic Absorption
Absorption in the UV and Atoms in the gaseous state can absorb ultraviolet or visible radiation or x-rays and
visible regions leads to result in a spectrum consisting of a number of very sharp absorption lines,
the transition of characteristic of the atomic species. This is called a line spectrum. Let us consider the
outermost electrons while simple case of absorption by gaseous sodium atom. It exhibits two sharp absorption
X-ray absorption involves peaks in the yellow region of visible spectrum (589 nm and 589.6 nm) as shown in
the transition of electrons
closest to the nuclei of
Fig.1.12, consequent on excitation of 3s electron to two of the 3p states. Absorption in
atoms. the UV region on the other hand results in signals at 330 nm and 285 nm due to the
excitation of 3s election to 4p and 5p orbital respectively.

The atomic absorption

spectrum is composed of
a series of sharp and well
defined lines Fig. 1.12: Absorption spectrum of sodium vapours in the visible range
characteristic of each
element. Atomic absorption spectra of alkali and alkaline earth metals are simpler. On the other
hand the transition elements give rise to multitudes of lines, yet each element has its
own characteristic absorption lines and is useful for qualitative and quantitative
studies. You would learn about atomic absorption spectroscopy in detail in Unit 7 of
this course.
Each electronic energy
level is associated with Molecular Absorption
several vibrational levels
and each of the Absorption by molecules is more complex than by atoms, as there are a large number
vibrational level is of energy states possible in case of molecules. You would recall that in case of
associated with several of molecules the vibration and rotation motion is also quantised in addition to electronic
the rotational energy motion. A molecular energy level in fact has three components and its energy can be
levels, possible energy given by the following expression.
levels are much more for
molecules as compared to E = Eelectronic + Evibrational + Erotational
atoms.
Accordingly, three types of quantised transitions occur on excitation with radiations in
UV-VIS, IR and microwave regions respectively. The ultraviolet and visible radiations
20
cause transition of electrons from the low energy electronic states to the higher energy Electromagnetic
states. On the other hand, IR and microwave radiations cause transitions amongst the Radiation
vibrational and rotational energy levels, respectively.

Fig. 1.13: Simplified energy level diagram showing the reason for observing band
spectrum in the molecules
Since each electronic energy level is associated with several vibrational levels and
each of the vibrational level is associated with several of the rotational energy levels, Molecular spectrum
the transitions caused by UV-VIS radiation have associated vibrational and rotational generally consists of a
transitions. Accordingly the molecular spectra are quite complex and consist of a large series of closely spaced
absorption lines and
number of transitions. For this reason, electronic absorption bands for molecules are
appears as a band.
usually broad and the spectrum is called band spectrum. Fig.1.13 gives a simplified
energy level diagram for a molecule showing the reason for observing band spectrum.
Similarly the transitions caused by radiations in the IR region have an associated
rotational component. Sample IR and UV spectra are given in Fig. 1.14.

(a) (b)

Fig. 1.14: Sample a) IR spectrum and b) UV spectrum

Sometimes the sample does not absorb radiation of a given type under
ordinary conditions but on placing the sample in a magnetic field it
does. This phenomenon is of immense analytical applications and is
the origin of probably the most exploited molecular structure
21
Molecular Spectroscopic determination technique i.e., nuclear magnetic resonance (NMR).
Methods-I
Another important technique of ESR also need magnetic field. Let us
learn about the magnetic field induced absorption.

Magnetic Field Induced Absorption

The elementary particles such as electrons and nucleons are associated with magnetic
properties. When subjected to external strong magnetic field, the interactions between
the internal and external magnetic fields give rise to additional quantised energy
levels. The difference in the energies of these levels is small and transitions are
brought about by absorption of the radiation of longer wavelength ranges. The
transitions amongst the energy levels generated due to the interaction of the nuclear
magnetic moment with the applied magnetic field are studied using radio-waves in the
range of 30 to 500 MHz and give rise to Nuclear Magnetic Resonance (NMR)
spectroscopy. The energy separation of the levels created by interaction between the
electron magnetic moment with the applied external field is even smaller. These are
studied under Electron Spin Resonance (ESR) Spectroscopy by using microwaves
of a frequency of about 9500 MHz.
The intensity or radiant
power (P) of a line or You may be wondering that what happens to the absorbing species after it has
band is directly absorbed the photon. Where does this extra energy go? Does it bring in some kind of a
proportional to the change in the structure of the species? In other words, what is the fate of the absorbed
number of excited atoms
radiation?
or molecules present in
the system. This provides
a method for quantitative Fate of the Absorbed Radiation
determination of the As a consequence of the absorption, the energy of the photon is transferred to the
analyte. absorbing species and it acquires an excited state.
M + hν → M* (Excitation)
The concentration of the excited species so obtained is quite small and its life time is
very short. The excited species generally loses the extra energy to the other atoms or
molecules, present in the medium and reverts back to the ground state. This process is
called non-radiative relaxation and occurs in a short period of time (10 ‒6 to 10 ‒9 s).
The excess energy is transferred in a series of small steps to the neighboring species as
their kinetic energy and is manifested in the form of heat. As a consequence of this,
the temperature of the system increases slightly.
M* → M + heat (Relaxation)
In some cases the relaxation process is accompanied by an emission of radiation and is
referred to as radiative relaxation. Let us learn about different types of radiative
relaxation mechanisms and the spectra which arises due to these.

SAQ 5
Calculate the population of an energy level having energy of 10 kJ relative to the
ground state at 327oC.
…………………………………………………………………………………………
…………………………………………………………………………………………
…………………………………………………………………………………………
…………………………………………………………………………………………

1.4.2 Emission
During the festive season or at the times of celebrations, you must have enjoyed the
beautiful display of colours by fireworks in the sky. This splendid show is a result of
relaxation of excited species from higher energy to the ground level releasing the

22
excess energy in the form of light and heat. The colours we see are electromagnetic Electromagnetic
radiations in the visible range. The excitation of the species can be brought about by a Radiation
number of ways, such as, absorption of electromagnetic radiation, bombardment with
electrons or other elementary particles, exposure to high potential alternating current,
spark, arc or a flame. The radiation emitted by an excited species is characterised in
terms of an emission spectrum. Like an absorption spectrum, the emission spectra
may be a band spectrum or a line spectrum. Fig.1 .15 shows a schematic emission
spectrum.

Fig. 1.15: A schematic emission spectrum

The line spectrum is a result of relaxation of atoms or ions and generally consists of a
series of well defined lines characteristic of the species involved. On the other hand,
the band spectra, which consist of several groups of lines that are closely spaced and
not resolved, are given by excited molecules or radicals. In case of incandescent
solids we get continuous spectra wherein the line spectra and band spectra are
superimposed and appear as a continuum. Let us learn about these types of spectra.

Line Spectra
Line spectra are obtained from individual atoms that are well separated in a gaseous
sample of an element. The atomised sample of the element is subjected to a flame,
plasma, an electric arc or spark whereby the constituent atoms are excited to higher
orbitals. For example, in case of sodium atom, single outer electron in the 3s orbital
can be excited to higher orbitals. The excited state being unstable and short lived,
returns to the ground state by the emission of a photon. The emission from the first
excited state (3p) of sodium is responsible for the yellow colour emission at 589.6 nm
of the flame when sodium salts are introduced into it. Other excited states
corresponding to 4p and 5p levels give emissions at 330.6 nm and 285.3 nm
respectively in the ultraviolet region. The flame emission and atomic emission
spectroscopic techniques are based on this phenomenon and are useful for qualitative
and quantitative measurement of atoms. You would learn about these in the third
block of the course.

Band Spectra
Band spectra arise from gaseous radicals or small molecules and consist of a series of
closely spaced lines that arise from the radiative relaxation of the excited molecule to
any of the available vibrational levels in the ground state Fig. 1.16 illustrates the origin
of band spectrum of a molecule. You may note here that the molecule in the
vibrational ground state of the excited electronic state may relax to any of the five
vibrational levels of the ground state shown here. Accordingly the emission spectrum
would consist of five closely spaced lines in the example given here. In complex

23
Molecular Spectroscopic molecules, the emission band consists of many more lines that are much more closely
Methods-I
spaced and appear as a band.

Fig. 1.16: Emission band spectrum of a molecule

Continuous Spectra
As mentioned earlier, the continuous spectra are caused by solids when heated. It is
characteristic of the temperature of the emitting surface rather than the bulk of the
material. These types of spectra are produced by condensed solids giving rise to
innumerable atomic and molecular oscillations. Heated solids are used as radiation
sources of analytical instruments involving IR, visible and longer wavelength UV
radiations.

Fluorescence and Phosphorescence

In the emission spectra of atoms and molecules discussed above the energy of the
emitted radiation is same as that used for excitation. In some atomic and molecular
systems the emitted radiation is of different frequency than that of the excitation
radiation. These are either due to fluorescence or phosphorescence. In such
emissions, the excited atom or molecule does not emit radiation directly from the
excited state. Instead the excited species relaxes down to excited state of lower energy
through non-radiative processes and then from there it comes to the ground state
accompanied by the emission of radiation. You would learn these analytically
important phenomena in details in Units 5 and 6 of this course.

1.4.3 Raman Scattering

You have read in the subsection 1.3.5 that, when a radiation interacts with matter a
part of it gets scattered. If a monochromatic radiation is used then the scattered
radiation is of the same frequency as the incident frequency. This is called Rayleigh
scattering. However, it has been found that in certain cases the radiation may interact
with matter in such a way that it involves certain amount of energy exchange.
Consequently the scattered radiation has frequencies greater or smaller than that of the
incident radiation. This is called Raman scattering and is an important analytical
tool. You would learn in details about Raman spectroscopy, which is based on this
type of scattering, in Unit 4 of this course.

SAQ 6
What is the difference between the radiative and non radiative relaxations?
…………………………………………………………………………………………
…………………………………………………………………………………………
…………………………………………………………………………………………

24
We have so far learnt that the radiation can interact in different ways with the matter Electromagnetic
and cause transitions amongst different types of quantised energy levels. Table 1.2 Radiation
summarises different types of spectroscopies, the regions of the wavelength
responsible for them and the nature of quantum transitions involved in them. We shall
take up different spectroscopic methods in the forthcoming units.

Table 1.2: Spectroscopic methods based on wavelength range and the type of
quantum transitions involved
Type of spectroscopic Wavelength range Type of quantum transition
method
Mossbauer spectroscopy 0.005 – 1.4 Å Nuclear transition (change of
(γ-ray spectroscopy) nuclear configuration)

X-ray (Diffraction, 0.1 - 100 Å Inner electron transition

Absorption, Emission, (change of electron
Fluorescence) distribution)

Vacuum UV absorption 10 - 180 nm Bonding electrons transition

(change of electron
distribution)
UV and Visible 180 - 780 nm Bonding electrons transition
(Absorption, Emission, (change of electron
Fluorescence) distribution)
Infrared (Absorption) and 0.78 - 300 nm Vibration/Rotation of
Raman (Scattering) molecules (change of
configuration)
Microwave absorption 0.75 - 3.75 nm Rotation of molecules.
(change of orientation)

Nuclear Magnetic Resonance 0.6 - 10 m Spin of nuclei in a magnetic

(NMR) field (change of nuclear spin)
Electron Spin Resonance 3 cm Spin of electrons in a
(ESR) magnetic field (change of
electron spin)

We will begin with the UV-visible spectroscopy in the next unit.

1.5 SUMMARY
Electromagnetic radiation is the radiant energy which is transmitted through space at
enormous velocities and does not require a medium for transmission and readily pass
through vacuum. According to wave mechanical model it can be visualised as
oscillatory electric and magnetic fields travelling in the planes perpendicular to each
other and also to the direction of propagation. These waves are characterised by a
number of parameters like, amplitude, wavelength, frequency, wavenumber, velocity,
energy etc. On the other hand according to the quantum or particle model, the radiant
energy is considered as stream of discrete particles or packets of energy called as
quanta, whose energy is proportional to its frequency.

The wave nature of electromagnetic radiation is manifested in terms of a number of

phenomena. Interference refers to the interaction of two waves as they are travelling.
The result of such an interaction depends on whether they interact constructively or
destructively. Diffraction is a consequence of interference and refers to the
phenomenon of bending of a wave round the corners of sharp barriers or through
narrow openings.

When EM radiation passes through a transparent medium, its velocity is reduced due
to the interaction of radiation with the constituents of matter. The extent of interaction
is expressed in terms of the refractive index of the medium. The variation of refractive
index of a substance with wavelength of the radiation is called as dispersion.
25
Molecular Spectroscopic
Methods-I
When a radiation passes from a given medium to another medium it bends towards or
away from the normal to the interface. This is called refraction and is due to the
difference in the velocities of the radiation in the two media. A fraction of the
radiation however, bounces back at an angle equal to the angle of incidence of the
radiation and is termed as reflection.

Ordinary radiation is unpolarised radiation and consists of a bundle of electromagnetic

waves having vibrations among an infinite series of planes perpendicular to the
direction of propagation. On passing ordinary light through a polariser we can get
polarised light having vibrations in a single plane.

The interaction of radiation with matter causes transitions among the quantised energy
levels of the interacting species. When a radiation falls on the matter it may either be
absorbed or it may excite the interacting species which then may emit a radiation or
the radiation undergoes scattering as a consequence of interaction.

The absorption or emission spectra of atomic species consist of a series of discrete

lines and is called a line spectrum. On the other hand the molecular spectra are quite
complex and the resulting spectra are usually broad and the spectrum is called band
spectrum.

The radiations in the different regions of the EM spectrum have different energies. On
interacting with the matter these cause transitions amongst different types of quantised
energy levels. This leads to different types of spectroscopies.

1.6 TERMINAL QUESTIONS

1. Name the phenomena which could not be explained on the basis of wave
mechanical model of EM radiation.
2. What is an electromagnetic radiation? List any three characteristics of
electromagnetic radiation.
3. Explain the following in brief.
a) Constructive interference
b) Destructive interference
c) Reflection of light
d) Refraction of light
4. Express the wavelength 3500 Å in terms of micrometres and nanometres.
5. Calculate the frequency and wave number for the EM radiation having a
wavelength of 10 m.
6. Compute and compare the energies of the photon corresponding to the FM radio
frequencies of your region.
7. Atomic spectrum consists of sharp lines whereas molecular spectrum contains
broad bands. Explain.
8. Name the type of transitions involved in the UV-Visible, IR, and Microwave
spectroscopic techniques?

1.7 ANSWERS

Self Assessment Questions

1. The electromagnetic radiations do not need a medium for transmission; these
can transmit through vacuum. However, for sound waves a medium is necessary
for transmission.

26
 hc Electromagnetic
2. We know that E = hν = Radiation
λ
h = 6.626 × 10−34 J s
c = 3.0 × 108 m s−1
λ = 535 × 10−9 m
Substituting the values, we get
6.626 × 10 −34 J s × 3.0 × 10 8 m s −1
E= = 3.72 × 10 −19 J
5.35 × 10 −7 m
3. The phenomenon of bending of a wave round the corners of sharp barriers or
through narrow openings is called diffraction.
The extent of diffraction varies inversely with the width of the slit and is
observable only when the size of the slit is comparable to that of the wavelength
of the light.
4. Plane polarised light is that EM radiation in which the electrical (also magnetic )
field oscillates in a single plane. These can be obtained by passing the
unpolarised radiation through a polariser made up of calcite or quartz crystals.
∆E
Ni −
5. According to Boltzmann distribution, = e kT
N0
Given: ∆E = 10 kJ; T= 327o C = 327 + 273 = 600 K
We are given the value of ∆E per mole; first we calculate it per molecule by
dividing it with Avogadro’s constant
10 × 10 3 J mol −1
∆E = E f − E i = = 1.66 × 10−20 J
6.022 × 10 23 mol −1
Now substituting it in the Boltzmann formula, we get
∆E 1.66×10 −20 J
Ni − −
= e kT = e 1.38×10 JK ×300 K = e−4.10 = 0.0166
− 23 −1

N0
6. These relaxations refer to the mechanisms by which an excited species relaxes
to the ground state. The radiative relaxation is accompanied by the emission of a
photon whereas in non-radiative relaxation the energy is emitted as heat.

Terminal Questions
1. The wave mechanical model of electromagnetic radiations could not explain the
phenomenon of absorption, emission and scattering of radiant energy.
2. Electromagnetic radiation is a kind energy which is transmitted through space in
the form of electric and magnetic fields. It travels with the speed of light and
does not need any medium to travel.
The different characteristics of electromagnetic radiation are
• Amplitude
• Wavelength
• Frequency
• Wave number
• Velocity

27
Molecular Spectroscopic 3. The terms can be explained as follows:
Methods-I
Constructive Interference
When two waves travelling together are in phase then these reinforce each other.
The amplitude of the resultant wave is more than that of any of the two waves.
In fact it is the sum of the amplitudes of the two waves.

Destructive Interference
When two waves travelling together are out of phase then these cancel each
other. The amplitude of the resultant wave is equal to the sum of the amplitudes
of the two waves. In case the waves are completely out of phase the waves are
destroyed completely.

Reflection of Light
When a radiation travelling in a given medium is incident on a medium of
different refractive index at an angle; then a fraction of the radiation bounces
back at an angle equal to the angle of incidence of the radiation. This is called
reflection of light.

Refraction of Light
The change in the direction of a beam of light when it falls on the interface of
two transparent media of different densities is called refraction.
4. We know that 1Å = 1×10 −10 m
So 3500 Å = 3500 × 10 −10 m
We can write it as = 0.35 × 104 × 10−10 m = 0.35 × 10 −6 m = 0.35 µm
Similarly, we can write
3500 Å = 350 × 10 ×10 −10 m = 350 × 10 −9 m = 350 nm
c
5. We know that ν = and c = 3.0 × 1010 m s−1
λ
Substituting the values, we get
3.0 × 1010 m s −1
ν= = 3.0 × 10 9 s −1 = 3.0 × 109 Hz.
10 m

1
Further, as wavenumber and wavelength are related as, ν =
λ
Substituting the values of the wavelength we get, wave number

28
 1 Electromagnetic
ν= = 0.1 m −1 Radiation
10 m
6. Energy and frequency are related as E = hν
The frequencies of the FM radio stations range from about 90 to 108 MHz; let
us take the frequencies of two FM stations as ν1 and ν 2 MHz, respectively
The energies of the photons corresponding to the radio frequencies of the two
stations would be hν1 and hν 2 respectively and can be calculated by
substituting the values of h and the frequency.
E 2 hν 2 ν 2
The ratios of the energies can be calculated as = =
E1 hν1 ν1
You may substitute the values corresponding to the FM radio frequencies of
your region and compute the ratio.
7. In case of atomic spectrum the transitions occur from one electronic energy
level to the other and result in sharp lines.
On the other hand, in case of molecules the vibration and rotation motion is also
quantised, and each electronic energy level is associated with several vibrational
levels and each of the vibrational level is associated with several of the
rotational energy levels.
Thus, the electronic transitions in the molecules have associated vibrational and
rotational transitions and radiations over a range of wavelengths are absorbed.
Therefore, the molecular absorption spectra have broad bands.
8. UV-Visible : electronic
IR : vibrational
Microwave : rotational

29