Spectroscopy

Spectroscopy, study of the absorption and emission of light and other radiation by matter, as
related to the dependence of these processes on the wavelength of the radiation. 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.

Spectroscopic techniques have been applied in virtually all technical fields

of science 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 the universe is thought to have originated (see below Survey of
optical spectroscopy: General principles: Applications). The internal structure of
the proton and neutron and the state of the early universe up to the first thousandth of a second of
its existence are being unraveled with spectroscopic techniques using 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 different isotopes 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 frequency being 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 ν by the relation E = hν,
where h is Planck’s constant, spectroscopy is actually the measure of the interaction of photons
with matter as a function of the photon 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 approximate frequency range

(metres) (hertz)

radio waves 10–1,000 3 × 105–3 × 107

television waves 1–10 3 × 107–3 × 108

microwaves, radar 1 × 10−3–1 3 × 108–3 × 1011

infrared 8 × 10−7–1 × 10−3 3 × 1011–4 × 1014

visible light 4 × 10−7–7 × 10−7 4 × 1014–7 × 1014

ultraviolet 1 × 10−8–4 × 10−7 7 × 1014–3 × 1016

X-rays 5 × 10−12–1 × 10−8 3 × 1016–6 × 1019

gamma rays (γ
<5 × 10−12 >6 × 1019
rays)

An example of particle spectroscopy is a surface analysis technique known as electron energy loss
spectroscopy (EELS) that measures the energy lost when low-energy electrons (typically 5–
10 electron volts) collide with a surface. Occasionally, the colliding electron loses energy by
exciting the surface; by measuring the electron’s 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.
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Basic features of electromagnetic radiation
Electromagnetic radiation is composed of oscillating electric and magnetic fields that have the
ability to transfer energy through space. The energy propagates as a wave, 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 × 10−7 and 8 × 10−7 metre (1.6 × 10−5 and 3.1 ×
10−5 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 10−16 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 Å) is 10−10 metre, which is also the
typical diameter of an atom. One nanometre (nm) is 10 −9 metre. The micrometre (μm), which
equals 10−6 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 below Practical considerations: Methods of
dispersing spectra) are capable of resolving wavelengths as close as 10−3 nanometre, while
modern laser techniques can resolve optical wavelengths separated by less than 10−10 nanometre.

The frequency with which the electromagnetic wave oscillates is also used to characterize the
radiation. The product of the frequency (ν) and the wavelength (λ) is equal to the speed of light (c);
i.e., νλ = 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.)
Basic properties of atoms

An isolated atom can be described in terms of certain discrete states called quantum states.
Each quantum state has a definite energy associated with it, but several quantum states can have
the same energy. These quantum states and their energy levels are calculated from the basic
principles of quantum mechanics. For the simplest atom, hydrogen, which consists of a
single proton and a single electron, the energy levels have been calculated and tested to an
uncertainty of better than one part in 1011, but for atoms with many electrons, the accuracy of the
calculations may not be much better than a few percent of the energy of the levels.

Atomic energy levels are typically measured by observing transitions between two levels. For
example, an atom in its lowest possible energy state (called the ground state) can be excited to a
higher state only if energy is added by an amount that is equal to the difference between the two
levels. Thus, by measuring the energy of the radiation that has been absorbed by the atom, the
difference in its energy levels can be determined. The energy levels are identical for atoms of the
same type; allowed energies of a particular atom of silver are equal to those for any other atom of
the same isotope of silver.

Other isolated systems, including molecules, ions (charged atoms or molecules), and atomic
nuclei, have discrete allowed energies. The analysis of these simple systems is carried out with
techniques that are analogous to those that were first applied to simple atomic spectra. More
complex structures, such as clusters of atoms, and bulk condensed matter, such
as solids and liquids, also have energy levels describable by quantum mechanics. The energy
levels in these complex systems, however, are so closely spaced that they smear into a continuous
band of energies. Transitions between these bands allow researchers to discern many important
properties of a given material. The location and properties of the energy states are often referred
to as the electronic structure of the material. By comparing spectroscopic measurements
to quantum mechanical calculations based on an assumed model of the material, one can use
knowledge of a material’s electronic structure to determine its physical structure.

If an atom in its ground state is given some amount of energy so that it is promoted to an excited
state, the atom will release that extra energy spontaneously as it moves back into lower states,
eventually returning to the ground state. For an isolated atom, the energy is emitted
as electromagnetic radiation. The emitted energy E equals the upper-state energy minus the lower-
state energy; this energy is usually carried by a single quantum of light (a photon) having
a frequency ν in which photon energy (E) is equal to a constant times the frequency, E = hν,
where h, Planck’s constant, equals 6.626 × 10−34 joule second. This relationship determines the
frequencies (and wavelengths, because λ = c/ν) of light emitted by atoms if the energies of the
states are known. Conversely, the relationship allows the energy states of an atom to be determined
from measurements of its frequency or wavelength spectrum. The analysis of the discrete
wavelengths emitted or absorbed by an atom or molecule was historically carried out using prism
or grating spectrometers; because of the appearance of the separated light in these instruments,
these discrete wavelengths are sometimes called spectral lines.
Historical survey
The basis for analytical spectroscopy is the discovery, made in 1859 by the German
physicist Gustav R. Kirchhoff, that each pure substance has its own characteristic spectrum.
Another German physicist, Joseph von Fraunhofer, repeating more carefully an earlier experiment
by a British scientist, William Wollaston, had shown in 1814 that the spectrum of
the Sun’s electromagnetic radiation does not grade smoothly from one colour to the next but has
many dark lines, indicating that light is missing at certain wavelengths because of absorption.
These dark lines, sometimes called Fraunhofer lines, are also collectively referred to as
an absorption spectrum. The spectra of materials that were heated in flames or placed in electric-
gas discharges were studied by many scientists during the 18th and 19th centuries. These spectra
were composed of numerous bright discrete lines, indicating that only certain wavelengths were
present in the emitted light. They are called brightline, or emission, spectra.

Although the possibility that each chemical element has a unique characteristic spectrum had been
considered by numerous investigators, the early studies were hampered by the difficulty of
obtaining relatively pure substances. Any sample could contain impurities that would result in the
simultaneous production of many spectra. By using carefully purified substances, Kirchhoff
demonstrated characteristic spectra and initiated the technique of spectroscopic analysis of the
chemical composition of matter. The technique was applied by Kirchhoff and his colleague the
German chemist Robert Bunsen in 1861 to the analysis of the Sun’s electromagnetic spectrum and
the identification of the chemical elements in the Sun.