METHODS OF DISPERSING SPECTRA

A spectrometer, as mentioned above, is an instrument used to analyze the

transmitted light in the case of absorption spectroscopy or the emitted light in
the case of emission spectroscopy. It consists of a disperser that breaks the
light into its component wavelengths and a means of recording the relative
intensities of each of the component wavelengths. The main methods
for dispersing radiation are discussed here.

REFRACTION
Historically glass prisms were first used to break up or disperse light into its
component colours. The path of a light ray bends (refracts) when it passes from one
transparent medium to anothere.g., from air to glass. Different colours
(wavelengths) of light are bent through different angles; hence a ray leaves a prism in
a direction depending on its colour (see Figure 3). The degree to which a ray bends at
each interface can be calculated from Snells law, which states that if n1 and n2are the
refractive indices of the medium outside the prism and of the prism itself,
respectively, and the angles i and r are the angles that the ray of a given wavelength
makes with a line at right angles to the prism face as shown in Figure 3, then the
equation n1 sin i = n2 sin r is obtained for all rays. The refractive index of a medium,
indicated by the symbol n, is defined as the ratio of the speed of light in a vacuum to
the speed of light in the medium. Typical values for n range from 1.0003 for air at 0
C and atmospheric pressure, to 1.51.6 for typical glasses, to 4 for germanium in the
infrared portion of the spectrum.
Since the index of refraction of optical glasses varies by only a few percent across the
visible spectrum, different wavelengths are separated by small angles. Thus, prism
instruments are generally used only when low spectral resolution is sufficient.

DIFFRACTION
At points along a given wavefront (crest of the wave), the advancing light wave can
be thought of as being generated by a set of spherical radiators, as shown in Figure
4A, according to a principle first enunciated by the Dutch scientist Christiaan
Huygens and later made quantitative by Fraunhofer. The new wavefront is defined by
the line that is tangent to all the wavelets (secondary waves) emitting from the
previous wavefront. If the emitting regions are in a plane of infinite extent, the light
will propagate along a straight line normal to the plane of the wavefronts. However, if
the region of the emitters is bounded or restricted in some other way, the light will
spread out by a phenomenon called diffraction.

Diffraction gratings are composed of closely spaced transmitting slits on a flat surface
(transmission gratings) or alternate reflecting grooves on a flat or curved surface
(reflection gratings).
If collimated light falls upon a transmission grating, the wavefronts successively pass
through and spread out as secondary waves from the transparent parts of the grating.
Most of these secondary waves, when they meet along a common path, interfere with
each other destructively, so that light does not leave the grating at all angles. At some
exit angles, however, secondary waves from adjacent slits of the grating are delayed
by exactly one wavelength, and these waves reinforce each other when they meet
i.e., the crests of one fall on top of the other. In this case,constructive
interference takes place, and light is emitted in directions where the spacing between
the adjacent radiators is delayed by one wavelength (see Figure 4B). Constructive
interference also occurs for delays of integral numbers of wavelengths. The light
diffracts according to the formula m = d(sin i sin r), where iis the incident
angle, r is the reflected or transmitted angle, d is the spacing between grating slits, is
the wavelength of the light, and m is an integer (usually called theorder of
interference). If light having several constituent wavelengths falls upon a grating at a
fixed angle i, different wavelengths are diffracted in slightly different directions and
can be observed and recorded separately. Each wavelength is also diffracted into
several orders (or groupings); gratings are usually blazed (engraved) so that a
particular order will be the most intense. A lens or concave mirror can then be used to
produce images of the spectral lines.
As the grating in a spectrometer is rotated about an axis parallel to the slit axis, the
spectral lines are transmitted successively through the instrument. An
electronicphotodetector placed behind the slit can then be used to measure the amount
of light in each part of the spectrum. The advantage of such an arrangement is that
photodetectors are extremely sensitive, have a fast time response, and respond linearly
to the energy of the light over a wide range of light intensities (see belowOptical
detectors).

ractical considerations
GENERAL METHODS OF SPECTROSCOPY
Production and analysis of a spectrum usually require the following: (1) a source oflight (or other
electromagnetic radiation), (2) a disperser to separate the light into its component wavelengths,
and (3) a detector to sense the presence of light afterdispersion. The apparatus used to accept
light, separate it into its component wavelengths, and detect the spectrum is called
a spectrometer. Spectra can be obtained either in the form of emission spectra, which show one
or more bright lines or bands on a dark background, or absorption spectra, which have a
continuously bright background except for one or more dark lines.

Absorption spectroscopy measures the loss of electromagnetic energy after it illuminates the
sample under study. For example, if a light source with a broad band of wavelengths is directed
at a vapour of atoms, ions, or molecules, the particles will absorb those wavelengths that can
excite them from one quantum state to another. As a result, the absorbed wavelengths will be
missing from the original light spectrum after it has passed through the sample. Since most atoms
and many molecules have unique and identifiable energy levels, a measurement of the missing
absorption lines allows identification of the absorbing species. Absorption within a continuous
band of wavelengths is also possible. This is particularly common when there is a high density of
absorption lines that have been broadened by strong perturbations by surrounding atoms
(e.g., collisions in a high-pressure gas or the effects of near neighbours in a solid or liquid).
In the laboratory environment, transparent chambers or containers with windows at both ends
serve as absorption cells for the production of absorption spectra. Light with a continuous
distribution of wavelength is passed through the cell. When a gas or vapour is introduced, the
change in the transmitted spectrum gives the absorption spectrum of the gas. Often, absorption
cells are enclosed in ovens because many materials of spectroscopic interest vaporize
significantly only at high temperatures. In other cases, the sample to be studied need not be
contained at all. For example, interstellar molecules can be detected by studying the absorption
of the radiation from a background star.

ICATIONS
Spectroscopy is used as a tool for studying the structures of atoms and molecules. The
large number of wavelengths emitted by these systems makes it possible to investigate
their structures in detail, including the electron configurations of ground and various
excited states.
Spectroscopy also provides a precise analytical method for finding the constituents in
material having unknown chemical composition. In a typical spectroscopic analysis, a
concentration of a few parts per million of a trace element in a material can be
detected through its emission spectrum.
In astronomy the study of the spectral emission lines of distant galaxies led to the
discovery that the universe is expanding rapidly and isotropically (independent of
direction). The finding was based on the observation of a Doppler shift of spectral
lines. The Doppler shift is an effect that occurs when a source of radiation such as a
star moves relative to an observer. The frequency will be shifted in much the same
way that an observer on a moving train hears a shift in the frequency of the pitch of a
ringing bell at a railroad crossing. The pitch of the bell sounds higher if the train is
approaching the crossing and lower if it is moving away. Similarly, light frequencies
will be Doppler-shifted up or down depending on whether the light source is

approaching or receding from the observer. During the 1920s, the American
astronomer Edwin Hubble identified the diffuse elliptical and spiral objects that had
been observed as galaxies. He went on to discover and measure a roughly linear
relationship between the distance of these galaxies from the Earth and their Doppler
shift. In any direction one looks, the farther the galaxy appears, the faster it is receding
from the Earth.
Spectroscopic evidence that the universe was expanding was followed by the
discovery in 1965 of a low level of isotropic microwave radiation by the American
scientists Arno A. Penzias and Robert W. Wilson. The measured spectrum is identical
to the radiation distribution expected from a blackbody, a surface that can absorb all
the radiation incident on it. This radiation, which is currently at a temperature of 2.73
kelvin (K), is identified as a relic of the big bang that marks the birth of the universe
and the beginning of its rapid expansion.

Practical considerations
lternative title: spectral analysis

TABLE OF CONTENTS
Introduction
Survey of optical spectroscopy
o
o

General principles
Practical considerations

Foundations of atomic spectra

o
o
o
o
o

Basic atomic structure

Hydrogen atom states
The periodic table
Atomic transitions
Perturbations of levels

Molecular spectroscopy
o
o
o
o

General principles
Theory of molecular spectra
Experimental methods
Fields of molecular spectroscopy

X-ray and radio-frequency spectroscopy

o
o

X-ray spectroscopy
Radio-frequency spectroscopy

Resonance-ionization spectroscopy
o
o
o
o
o

Ionization processes
Atom counting
Resonance-ionization mass spectrometry
RIS atomization methods
Additional applications of RIS

Spectroscopy, study of the absorption and emission of light and

other radiation bymatter, as related to the dependence of these processes on
the wavelength of theradiation. More recently, the definition has been
expanded to include the study of the interactions between particles such
as electrons, protons, and ions, as well as their interaction with other particles
as a function of their collision energy. Spectroscopic analysis has been crucial
in the development of the most fundamental theories in physics,
including quantum mechanics, the special and general theories of relativity,
and quantum electrodynamics. Spectroscopy, as applied to high-energy
collisions, has been a key tool in developing scientific understanding not only
of the electromagnetic force but also of the strong and weak nuclear forces.

IMAGES

QUIZZES

LISTS

Spectroscopic techniques have been applied in virtually all technical fields

ofscience and technology. Radio-frequency spectroscopy of nuclei in a
magnetic field has been employed in a medical technique called magnetic
resonance imaging (MRI) to visualize the internal soft tissue of the body with
unprecedented resolution.Microwave spectroscopy was used to discover the
so-called three-degree blackbody radiation, the remnant of the big
bang (i.e., the primeval explosion) from which theuniverse is thought to have
originated (see below Survey of optical spectroscopy: General principles:
Applications). The internal structure of the proton and neutronand the state of
the early universe up to the first thousandth of a second of its existence is
being unraveled with spectroscopic techniques utilizing high-energy particle
accelerators. The constituents of distant stars, intergalactic molecules, and
even the primordial abundance of the elements before the formation of the
first stars can be determined by optical, radio, and X-ray spectroscopy. Optical
spectroscopy is used routinely to identify the chemical composition of matter
and to determine its physical structure.
Spectroscopic techniques are extremely sensitive. Single atoms and even
differentisotopes of the same atom can be detected among 1020 or more
atoms of a different species. (Isotopes are all atoms of an element that have
unequal mass but the same atomic number. Isotopes of the same element are
virtually identical chemically.) Trace amounts of pollutants or contaminants are
often detected most effectively by spectroscopic techniques. Certain types
of microwave, optical, and gamma-ray spectroscopy are capable of measuring

infinitesimal frequency shifts in narrow spectroscopic lines. Frequency shifts

as small as one part in 1015 of the frequencybeing measured can be observed
with ultrahigh resolution laser techniques. Because of this sensitivity, the most
accurate physical measurements have been frequency measurements.
Spectroscopy now covers a sizable fraction of the electromagnetic spectrum.
The table summarizes the electromagnetic spectrum over a frequency range
of 16 orders of magnitude. Spectroscopic techniques are not confined
to electromagnetic radiation, however. Because the energy E of a photon (a
quantum of light) is related to its frequency by the relation E = h, where h is
Plancks constant, spectroscopy is actually the measure of the interaction of
photons with matter as a function of thephoton energy. In instances where the
probe particle is not a photon, spectroscopy refers to the measurement of how
the particle interacts with the test particle or material as a function of the
energy of the probe particle.

Electromagnetic phenomena
approximate wavelength range
(metres)

approximate frequency range

(hertz)

radio waves

101,000

3 1053 107

television waves

110

3 1073 108

1 1031

3 1083 1011

infrared

8 1071 103

3 10114 1014

visible light

4 1077 107

4 10147 1014

ultraviolet

1 1084 107

7 10143 1016

X-rays

5 10121 108

3 10166 1019

<5 1012

>6 1019

microwaves,
radar

gamma rays
( rays)

An example of particle spectroscopy is a surface analysis technique known

aselectron energy loss spectroscopy (EELS) that measures the energy lost

when low-energy electrons (typically 510 electron volts) collide with a

surface. Occasionally, the colliding electron loses energy by exciting the
surface; by measuring the electrons energy loss, vibrational excitations
associated with the surface can be measured. On the other end of the
energy spectrum, if an electron collides with another particle at exceedingly
high energies, a wealth of subatomic particles is produced. Most of what is
known in particle physics (the study of subatomic particles) has been gained
by analyzing the total particle production or the production of certain particles
as a function of the incident energies of electrons and protons.
The following sections focus on the methods of electromagnetic spectroscopy,
particularly optical spectroscopy. Although most of the other forms of
spectroscopy are not covered in detail, they have the same common heritage
as optical spectroscopy. Thus, many of the basic principles used in other
spectroscopies share many of the general features of optical spectroscopy.

Survey of optical spectroscopy

General principles
BASIC FEATURES OF ELECTROMAGNETIC RADIATION
Electromagnetic radiation is composed of oscillating electric and magnetic
fieldsthat have the ability to transfer energy through space. The energy
propagates as awave, such that the crests and troughs of the wave move in
vacuum at the speed of 299,792,458 metres per second. The many forms of
electromagnetic radiation appear different to an observer; light is visible to the
human eye, while X rays and radio waves are not.
The distance between successive crests in a wave is called its wavelength.
The various forms of electromagnetic radiation differ in wavelength. For
example, the visible portion of the electromagnetic spectrum lies between 4
107 and 8 107metre (1.6 105 and 3.1 105 inch): red light has a longer
wavelength than green light, which in turn has a longer wavelength than blue
light. Radio waves can have wavelengths longer than 1,000 metres, while
those of high-energy gamma rays can be shorter than 1016 metre, which is
one-millionth of the diameter of an atom. Visible light and X rays are often
described in units of angstroms or in nanometres. One angstrom (abbreviated
by the symbol ) is 1010 metre, which is also the typical diameter of an atom.

One nanometre (nm) is 109 metre. The micrometre (m), which equals
106 metre, is often used to describe infrared radiation.
The decomposition of electromagnetic radiation into its component
wavelengths is fundamental to spectroscopy. Evolving from the first
crude prism spectrographs that separated sunlight into its constituent colours,
modern spectrometers have provided ever-increasing wavelength resolution.
Large-grating spectrometers (see belowPractical considerations: Methods of
dispersing spectra) are capable of resolving wavelengths as close as
103 nanometre, while modern laser techniques can resolve optical
wavelengths separated by less than 1010 nanometre.
The frequency with which the electromagnetic wave oscillates is also used to
characterize the radiation. The product of the frequency () and the
wavelength () is equal to the speed of light (c); i.e., = c. The frequency is
often expressed as the number of oscillations per second, and the unit of
frequency is hertz (Hz), where one hertz is one cycle per second. Since the
electromagnetic spectrum spans many orders of magnitude, frequency units
are usually accompanied by a Latin prefix to set the scale of the frequency
range. (See measurement system: The metric system of measurement: The
International System of Units for a table of the prefixes commonly used to
denote these scales.)