Spectroscopy
Absorption | Emission | Scattering
| Information Available from Various Spectroscopic Techniques
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Introduction
Spectroscopy is the use of the absorption, emission, or scattering of electromagnetic
radiation by atoms or molecules (or atomic or molecular ions) to qualitatively
or quantitatively study the atoms or molecules, or to study physical processes.
The interaction of radiation with matter can cause redirection of the radiation
and/or transitions between the energy levels of the atoms or molecules. A transition
from a lower level to a higher level with transfer of energy from the radiation
field to the atom or molecule is called absorption.
A transition from a higher level to a lower level is called emission
if energy is transfered to the radiation field, or nonradiative decay if no radiation
is emitted. Redirection of light due to its interaction with matter is called
scattering, and may or may not occur with transfer of
energy, i.e., the scattered radiation has a slightly different or the same wavelength.
When atoms or molecules absorb light, the incoming energy excites a quantized
structure to a higher energy level. The type of excitation depends on the wavelength
of the light. Electrons are promoted to higher orbitals by ultraviolet or visible
light, vibrations are excited by infrared light, and rotations are excited by
microwaves.
An absorption spectrum is the absorption of light as a function of wavelength. The spectrum of an atom or molecule depends on its energy level structure, and absorption spectra are useful for identifying of compounds.
Measuring the concentration of an absorbing species in a sample is accomplished
by applying the Beer-Lambert Law.
Atoms or molecules that are excited to high energy levels can decay to lower levels
by emitting radiation (emission or luminescence). For atoms excited by a high-temperature
energy source this light emission is commonly called atomic or optical emission
, and for atoms excited with light it is called atomic fluorescence. For molecules
it is called fluorescence if the transition is between states of the same spin
and phosphorescence if the transition occurs between states of different spin.
The emission intensity of an emitting substance is linearly proportional to
analyte concentration at low concentrations, and is useful for quantitating
emitting species.
When electromagnetic radiation passes through matter, most of the radiation continues
in its original direction but a small fraction is scattered in other directions.
Light that is scattered at the same wavelength as the incoming light is called
Rayleigh scattering. Light that is scattered in transparent solids due to vibrations
(phonons) is called Brillouin scattering. Brillouin scattering is typically shifted
by 0.1 to 1 cm-1 from the incident light. Light that is scattered due
to vibrations in molecules or optical phonons in solids is called Raman scattering.
Raman scattered light is shifted by as much as 4000 cm-1 from the incident
light.
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