Interaction with matter

Energy levels

Degrees of Freedom

Spectroscopy
Rotational Spectroscopy

Vibrational Spectroscopy

infrared

microwave

Electronic Transitions

Absorption Spectroscopy

Emission Spectroscopy

Introduction to Matters
Rotational Spectroscopy
Vibrational Spectroscopy
Absorption and emission Spectroscopy
Atkins, Physical Chemistry, 9th edition, 2009
Banwell & McCash, Fundamentals of Molecular Spectroscopy, 4th edition, 1996
Lakowicz, Principles of Fluorescence Spectroscopy, Springer Publishers, 3rd Edition, 2011
Moog, Spencer and farrell, Physical Chemistry: A Guided Inquiry: Atoms, Molecules,
and Spectroscopy, 2003

 The sun produces a full spectrum of electromagnetic

radiation

http://csep10.phys.utk.edu/astr162/lect/light/spectrum.html

http://kr.blog.yahoo.com/bmw26z/2188

Components of Electro Magnetic

Radiation

Two Components of EM
Radiation
Electrical field (E): varies in magnitude in a direction
perpendicular to the direction of propagation
Magnetic field (M): at right angle to the electrical
field, is propagated in phase with the electrical field
Wavelength (l), distance from one wave crest to another
Frequency (n), No. of crests passing a fixed point/ given time
Amplitude, height of each peak (watts/sq. meter

The speed of EM energy c 300,000km/second,

c = nl where l and n are inversely related

Interaction of radiation with matter

Wavelength
If there are no available quantized energy levels matching the quantum
energy of the incident radiation, then the material will be transparent to that
radiation

Molecular Transitions
for UV-Visible Absorptions
What electrons can we use for these
transitions?

Nature of Shift

Descriptive Term

To Longer
Wavelength

Bathochromic

To Shorter
Wavelength

Hypsochromic

To Greater
Absorbance

Hyperchromic

To Lower
Absorbance

Hypochromic

Absorption and Emission Spectroscopy

Introduction to Absorption
Reflection and Scattering Losses

LAMBERT-BEER LAW

Psolution
P
T

Psolvent
P0
P

A log T log
P0
A abc kc
a absorptivity
b pathlength
c concentration

Power of
radiation after
passing through
the solvent
Power of radiation
after passing
through the sample
solution

Problems

CY 515 (Spectroscopic Method of Analysis)

Dr. Priyabrat Dash
NIT Rourkela, India

23

Beers law and mixtures

Each analyte present in the solution absorbs light!

The magnitude of the absorption depends on its e
A total = A1+A2++An
A total = e1bc1+e2bc2++enbcn
If e1 = e2 = en then simultaneous determination is
impossible
Need nls where es are different to solve the mixture

Spectral nomenclature of shifts

Electronic Transitions in Molecules

Molecular Orbital (MO) Theory
for C2H4 molecule,

UV or Visible
spectral region

Fate of Excited Electronic States

Department of Chemistry, KAIST

Molecular Motion and Spectroscopy

Study of Interaction of Matter and Light (Photon)
Molecular Spectroscopy
Information about molecules such as geometry and energy
levels are obtained by the interaction of molecules and photons

Molecular motions: Translation, Rotation, Vibration

determines the energy levels for the absorption or emission of
photons

Electronic, Vibrational, and Rotational Energy Levels

of a Diatomic Molecule

Exercise: Indicate the

molecular state in which it is
electronically in the ground
state, vibrationally in the first
excited state, and rotationally
in the ground state.