Introduction to Spectroscopy
Spectroscopy is a general term referring to the
interactions of various types of electromagnetic
radiation with matter.
Exactly how the radiation interacts with matter is
directly dependent on the energy of the radiation.
The higher energy ultraviolet and visible wavelengths affect the energy levels of the
outer electrons.
Infrared radiation is absorbed by matter resulting in rotation and/or vibration of
molecules.
Radio waves are used in nuclear magnetic resonance and affect the spin of nuclei in a
magnetic field.
Electromagnetic Radiation
Electromagnetic Radiation: Kind of energy with
wave character that can be characterized by
using wavelength (), frequency (), velocity
and amplitude (A).
Electromagnetic radiation is a stream of
discrete particles or wave packets of energy
called photons where energy is proportional to
the frequency of the radiation.
Electromagnetic Radiation
Velocity of electromagnetic radiation in vacuum: 2.99792 * 108 m/s
Velocity
Amplitude
Frequency
Phase angle
Polarization
Direction of propagation
Electromagnetic Radiation
Wave Parameters
• Amplitude (A): Length of the electric vector at
the maximum in the wave.
• Period (P): The time in seconds required for the
passage of successive maxima or minima
through a fixed point in space.
• Frequency (): The number of oscillations of the
field that occur per second and is equal to 1/P.
(s-1 or Hz).
• Wavelength (): The linear distance between
any two equivalent points on successive waves
(successive maxima or minima).
• Velocity of propagation: V = x
In vacuum, the velocity of radiation is
independent of wavelength and given by the
symbol c.
c = = 3.00 x 108 m/s = 3.00 x 1010 cm/s
• Wavenumber (): The reciprocal of the
wavelength in centimeters (cm-1).
• The Electromagnetic Spectrum: The
electromagnetic spectrum encompasses an
enormous range of wavelength and
frequencies. Spectroscopic methods are
classified according to the wavelengths or
frequencies that are important for analytical
purpose.
Electromagnetic Spectrum
An Introduction to Spectrometric Methods
• Spectrometric methods are a large group of
analytical methods that are based on atomic and
molecular spectroscopy. Spectroscopy deals
with the interactions of various types of
radiation (mainly electromagnetic radiation)
with matter.
Interactions of Electromagnetic Radiation
• Physical Interactions: Not dependent on the
characteristic of electromagnetic radiation
1. Reflection
2. Refraction
3. Diffraction
4. Scattering
5. Polarization
• Chemical Interactions: Dependent of the
characteristics of electromagnetic radiation
Absorption of Radiation
• Absorption of Radiation: Absorption occurs
only if :-
a. There is an interaction between the
electromagnetic radiation and the material.
b. The energy of the electromagnetic radiation
must exactly correspond to the energy of
transition in the molecule.
Io → Sample → I
I < Io (absorption depends on population and
path length)
Planck’s Equation: The relationship
between frequency of light and energy E,
E = h ; where, h = Planck’s constant = 6.6 x
10-27 [Link] = 6.6 x 10-34 [Link]
In vacuum, velocity of light = c = = 3 x
1010cm/s which gives, = c/
E = h(c/) = hc (where, = 1/ = wave
number)
Energy directly proportional to wave
number
• Atomic Absorption: The passage of polychromatic
ultraviolet or visible radiation through a medium that
consists of monoatomic particles results in the
absorption of a few well-defined frequencies. Such
spectra are very simple due to the small number of
possible energy states for the absorbing particles.
• Molecular Absorption: Absorption spectra for
polyatomic molecules are considerably more complex
than atomic spectra because the number of energy states
of molecules is generally enormous when compared with
the number of energy states for isolated atoms. The
energy E of a molecule is made up of three components,
E = Eelectronic + Evibrational + Erotational
Absorption Spectrum
Absorption and Emission Spectra
Absorption Spectrum of some elements
In the second broad class of spectroscopic techniques, the
electromagnetic radiation undergoes a change in amplitude,
phase angle, polarization, or direction of propagation as a
result of its refraction, reflection, scattering, diffraction, or
dispersion by the sample.