Unit-2: D. Jim Livingston

LECTURE # 1:
Unit-2
SPECTROSCOPY - 1
by
D. JIM LIVINGSTON
ASST.PROF OF CHEMISTRY
St. JOHN’S COLLEGE
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WHAT IS
SPECTROSCOPY ?
THE STUDY OF THE INTERACTION BETWEEN ELECTROMAGNETIC

(EM) RADIATION AND MATTER
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ELECTROMAGNETIC RADIATION
Electromagnetic radiation is a form of energy

that is produced by oscillating electric and
magnetic disturbance
Electromagnetic radiation is one of the many
ways that energy travels through space.
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• VARIOUS FORMS OF
SUCH AS ULTRA-VIOLET, INFRA-
RED, X-RAYS, RADIO-WAVES ETC.
Consist of 2 waves oscillating

perpendicular to one another
scillating magnetic field
scillating electric field. 6

ew of the important characteristics of the electromagnetic radiation are
 The electric and magnetic components are mutually perpendicular to each other and
are coplanar.
 These are characterized by their wavelength of frequency of wavenumber.
 The energy carried by the an electromagnetic radiation is directly proportional to its

frequency. The emission or absorption of radiation is quantized and each quantum of
radiation is called a photon.
 All type of radiations travel with the same velocity and no medium is required for their
propagation. They can travel through vacuum.
 When visible light (a group of electromagnetic radiation ) is passed through a prism, it

is split up into seven colors which correspond to define wavelength to definite
wavelength. This phenomenon is called dispersion.
Wavelength , Wave number, Frequency ? 7
ELECTROMAGNETIC SPECTRUM
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THE ELECTROMAGNETIC SPECTRUM
• ELECTROMAGNETI
C WAVES CAN BE
CLASSIFIED AND
ARRANGED
ACCORDING TO
THEIR VARIOUS
WAVELENGTHS/FR
EQUENCIES; THIS
CLASSIFICATION
IS KNOWN AS THE
ELECTROMAGNETI
C SPECTRUM.
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WHAT HAPPENS TO MATTER?
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ABSORPTION AND EMISSION
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Absorptio
n
 If electromagnetic radiation (of certain wavelength range ) are passed
through the substrate under analysis of sometime, then radiation of certain
wavelengths are absorbed by the substrate.
 A dark pattern of lines which corresponds to the wavelengths absorbed is

called absorption spectra.
 In absorption spectra energy may heat up the sample or is re-emitted.
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Emission
 The excitation of atoms can be brought about thermally like heating the substrate
strongly or electrically like passing electric Discharge through the vapours of the
substrate at a very low pressure.
 When the electric discharge is passed through the vapours of the substrate,
energy is absorbed and electrons in the ground state are promoted to excited
states.
 When the electrons from the excited state jump to the lower energy state, then
some energy of definite frequency is released as a radiation.
 If this radiation is analysed with the help of spectroscope, an emission spectrum is

observed.
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DIFFERENT TYPES OF SPECTROSCOPY
• ATOMIC SPECTRA ARE THE TRANSITIONS OF ELECTRONS BETWEEN

ELECTRONIC ENERGY LEVELS IN ISOLATED ATOMS
• MOLECULAR SPECTRA INVOLVE TRANSITIONS IN MOLECULES WITH TWO
OR MORE ATOMS
• MOLECULAR SPECTRA HAVE ADDITIONAL MODES, ROTATIONAL AND
VIBRATIONAL THAT ARE A FUNCTION OF THE MOLECULAR STRUCTURE.
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TYPES OF MOLECULAR ENERGIES
• TRANSLATIONAL ENERGY:
• energy due to translational

motion of the molecule.
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• ROTATIONAL
ENERGY:
• energy associated
with the rotation of
the molecule about
its centre of gravity
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• VIBRATIONAL ENERGY:
• energy associated
with the vibrations of
the atoms
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• ELECTRONIC ENERGY
• transition of electron from

one energy level to another
energy level.
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Different Energy Levels
Vibrational levels
rotational levels
S1
Effects of the energy levels
depending on the nature of
the energy received
absorption
Energy
Vibrational levels
rotational levels
S0
Ground state
UV-Vis IR mW
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This work is licensed under a Creative Commons Attribution-Noncommercial-Share Alike 2.0 UK: England & Wales License
ENERGY LEVEL DIAGRAM
• E1, E2 – ELECTRONIC
STATES
• V0,V1 – VIBRATIONAL
STATES
• R1, R2 – ROTATIONAL
STATES
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MICROWAVE SPECTRA
• THIS SPECTROSCOPY UTILIZES PHOTONS IN THE MICROWAVE RANGE TO CAUSE
TRANSITIONS BETWEEN THE QUANTUM ROTATIONAL ENERGY LEVELS OF A GAS
MOLECULE.
• MICROWAVE REGION – 10-2 to 10 m
• Why Gas Phase?

• INTERMOLECULAR INTERACTIONS HINDERING ROTATIONS IN THE LIQUID AND SOLID
PHASES OF THE MOLECULE.
• Condition
• Molecule must posses a permanent dipole
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moment.
DIPOLE MOMENT
• A DIPOLE MOMENT IS A QUANTITY THAT DESCRIBES TWO OPPOSITE CHARGES

SEPARATED BY A DISTANCE
• BY DEFINITION THE DIPOLE MOMENT, Μ, IS THE PRODUCT OF THE MAGNITUDE OF
THE SEPARATED CHARGE AND THE DISTANCE OF THE SEPARATION
When atoms in a molecule share

electrons unequally, they create
what is called a dipole moment.
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WHICH MOLECULES EXHIBIT MICROWAVE
SPECTRA?
• HOMONUCLEAR DIATOMIC MOLECULES: MICROWAVE INACTIVE
• H2,O2, Cl2, CO2,C6H6 – ZERO DIPOLE MOMENT ( NO CHARGE SEPARATION)
• HETERONUCLEAR DIATOMIC MOLECULES: MICROWAVE ACTIVE

• HCl, HBr, CO, NO – PERMANENT DIPOLE MOMENT (CHARGE SEPARATION)
• SELECTION RULE:
• A SELECTION RULE, OR TRANSITION RULE, FORMALLY CONSTRAINS THE POSSIBLE
TRANSITIONS OF A SYSTEM FROM ONE QUANTUM STATE TO ANOTHER.
• SELECTION RULES HAVE BEEN DERIVED FOR ELECTROMAGNETIC TRANSITIONS IN
MOLECULES, IN ATOMS, IN ATOMIC NUCLEI, AND SO ON.
• FOR ROTATIONAL SPECTRA ΔJ = ±1.

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DERIVATION OF THE EXPRESSION FOR ROTATIONAL ENERGY
The rotations of a diatomic molecule can

be modeled as a rigid rotor.
The rigid rotor model has two masses
attached to each other with a fixed
distance between the two masses.
I – moment of inertia
ɷ - angular velocity
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Thank you
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LECTURE # 1:

THE STUDY OF THE INTERACTION BETWEEN ELECTROMAGNETIC

Electromagnetic radiation is a form of energy

Consist of 2 waves oscillating

scillating magnetic field

scillating electric field. 6

 These are characterized by their wavelength of frequency of wavenumber.

 The energy carried by the an electromagnetic radiation is directly proportional to its

 When visible light (a group of electromagnetic radiation ) is passed through a prism, it

 A dark pattern of lines which corresponds to the wavelengths absorbed is

 In absorption spectra energy may heat up the sample or is re-emitted.

 If this radiation is analysed with the help of spectroscope, an emission spectrum is

• ATOMIC SPECTRA ARE THE TRANSITIONS OF ELECTRONS BETWEEN

• energy due to translational

• transition of electron from

• Why Gas Phase?

• A DIPOLE MOMENT IS A QUANTITY THAT DESCRIBES TWO OPPOSITE CHARGES

When atoms in a molecule share

• H2,O2, Cl2, CO2,C6H6 – ZERO DIPOLE MOMENT ( NO CHARGE SEPARATION)

• HETERONUCLEAR DIATOMIC MOLECULES: MICROWAVE ACTIVE

• FOR ROTATIONAL SPECTRA ΔJ = ±1.

The rotations of a diatomic molecule can

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