Module – III

Spectroscopic Techniques and

Applications
 Spectroscopy
• Spectroscopy deals with the study of interaction of electromagnetic
radiation with matter

• It is the most powerful tool for the study of atomic and molecular structure
and is used in the analysis of wide range of materials

• It is the measurement and interpretation of electromagnetic radiation which

is absorbed or emitted by atoms or molecules

• This absorption or emission happens when the atoms of the sample move
from one energy state to another energy state in the presence of
electromagnetic radiation
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 Components of electromagnetic waves

A B

A) An electromagnetic wave showing orthogonal electric and magnetic components

B) Wavelength and amplitude
➢Electromagnetic radiation (EMR) is a simple harmonic wave of electric and
magnetic fields fluctuating orthogonal to each other
➢Interact with the electronic or magnetic energy level of molecules

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 EMR- Relation between energy and
wavelength

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 Electromagnetic spectrum
• The electromagnetic spectrum is a complete spectrum of all forms of “light”
• Electromagnetic spectrum consists of Radio waves, Microwaves, IR , UV, X-
ray, Gamma rays, etc

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 Types of energy present in Molecules
• A molecule can possess energies in different forms such as translational,
rotational energy, vibrational energy and electronic energy.
• Nuclei are so much more massive than the electrons, they must
accordingly have much smaller velocities with low energy.
• This separation of electronic and nuclear motion is known as the Born-
Oppenheimer approximation.
• A molecule can possess energies in different forms such as translational,
rotational energy, vibrational energy and, electronic energy.
E = Etrans + Erot + Evib+ Eelectron.
Eelectronic > Evibration > Erotation > Etranslational

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 EMR used in our day-to-day life
• Radio wave: Radio captures radio waves emitted by radio stations,
bringing your favourite tunes. Radio waves are also emitted by stars
and gases in space.
• Microwave: Microwave radiation will cook your popcorn in just a few
minutes, but is also used by astronomer to learn about the structure
of nearby galaxies.
• Infrared: Night vision goggles pick up the infrared light emitted by
our skin and objects with heat. In space, infrared light helps us map
the dust between stars.
• Visible: Our eyes detect visible light. Fire flies, light bulbs, and stars
all emit visible light.

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 Contd ……
• Ultraviolet: Ultraviolet radiation is emitted by the Sun and are the
reason for skin tans and burns. "Hot" objects in space emit UV
radiation as well.
• X-ray: A dentist uses X-rays to image your teeth, and airport
security uses them to see through your bag. Hot gases in the
Universe also emit X-rays.
• Gamma ray: Doctors use gamma-ray imaging to see inside your
body. The biggest Gamma-ray generator of all is the Universe.

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 Interaction of Electro-magnetic radiation
with matter
• To interact with the electromagnetic radiation, the molecules must have
some electric or magnetic effect that could be influenced by the electric or
magnetic components of the radiation.
• E&M radiation interacts with materials because electrons and molecules
in materials are polarizable
Atoms/molecules
Valence electrons

Core electrons

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 Interaction of electromagnetic radiation
with atom and molecule
• When a photon is absorbed
by a molecule it ceases to
exist and its energy is
transferred to the molecule.

• This energy can be

transferred to translational,
rotational, vibrational,
electronic forms.

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 Potential energy as a function of inter-
molecular distance
For a diatomic molecule, the electronic states can be represented by plots
of potential energy as a function of intermolecular distance
• Translational energy (Etrans) is concerned
with the overall movement of molecules
along the three axes. It is significant only in
gases.
• Rotational energy (Erot) –involves the
spinning of molecules about the axes
passing through their centre of gravity
• Vibrational energy (Evib) is associated with
vibration within the molecule such as
stretching or bending of the bonds
• Electronic energy (Eelec) involves promotion
of electron from lower energy state to
higherenergy state
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 Quantization of spectra
• The transition of electrons from one energy level to another energy level of
the atom results in emission or absorption of electromagnetic radiation
• The energy difference between the involved energy levels gives spectral
lines in different regions
• Molecules undergo processes like rotation, vibration, electronic transitions,
and nuclear transitions
• The energy changes within an atom or a molecule during absorption or
emission are quantized
• Spectrum originates from the atoms is called atomic spectra and spectrum
originate from the molecule is called molecular spectra

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 Types of spectra
Absorption Spectroscopy: Absorption spectra occur when energy from the
radiative source is absorbed by the material.

Emission spectroscopy: Emission indicates that radiative energy is released

by the material. Emission can also be induced by other sources of energy such
as block body radiation, flames or sparks or electromagnetic radiation in the
case of fluorescence.

Reflection and Scattering spectroscopy determine how incident radiation is

reflected or scattered by a material.
- Crystallography employs the scattering of high energy radiation, such as x-
rays and electrons to examine the arrangement of atoms in proteins and solid
crystals
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,
 Classification of spectroscopic techniques
• Electronic spectroscopy
• Atomic absorption spectroscopy
• Luminescence spectroscopy (Fluorescence spectroscopy)
• Inductively coupled plasma - atomic emission spectroscopy
(ICP-AES)
• Infrared spectroscopy
• NMR spectroscopy

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