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Emission
Origins

Radiation from molecules

Emission spectroscopy
History
Experimental technique in flame emission spectroscopy
Emission coefficient

Scattering of light
Spontaneous emission
See also
References
External links
Emission spectrum

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From Wikipedia, the free encyclopedia

Emission spectrum of a ceramic metal halide lamp.

A demonstration of the 589 nm D2 (left) and 590 nm D1 (right) emission sodium D

lines using a wick with salt water in a flame
The emission spectrum of a chemical element or chemical compound is the spectrum of
frequencies of electromagnetic radiation emitted due to electrons making a
transition from a high energy state to a lower energy state. The photon energy of
the emitted photons is equal to the energy difference between the two states. There
are many possible electron transitions for each atom, and each transition has a
specific energy difference. This collection of different transitions, leading to
different radiated wavelengths, make up an emission spectrum. Each element's
emission spectrum is unique. Therefore, spectroscopy can be used to identify
elements in matter of unknown composition. Similarly, the emission spectra of
molecules can be used in chemical analysis of substances.

Emission
In physics, emission is the process by which a higher energy quantum mechanical
state of a particle becomes converted to a lower one through the emission of a
photon, resulting in the production of light. The frequency of light emitted is a
function of the energy of the transition.

Since energy must be conserved, the energy difference between the two states equals
the energy carried off by the photon. The energy states of the transitions can lead
to emissions over a very large range of frequencies. For example, visible light is
emitted by the coupling of electronic states in atoms and molecules (then the
phenomenon is called fluorescence or phosphorescence). On the other hand, nuclear
shell transitions can emit high energy gamma rays, while nuclear spin transitions
emit low energy radio waves.

The emittance of an object quantifies how much light is emitted by it. This may be
related to other properties of the object through the Stefan–Boltzmann law. For
most substances, the amount of emission varies with the temperature and the
spectroscopic composition of the object, leading to the appearance of color
temperature and emission lines. Precise measurements at many wavelengths allow the
identification of a substance via emission spectroscopy.

Emission of radiation is typically described using semi-classical quantum

mechanics: the particle's energy levels and spacings are determined from quantum
mechanics, and light is treated as an oscillating electric field that can drive a
transition if it is in resonance with the system's natural frequency. The quantum
mechanics problem is treated using time-dependent perturbation theory and leads to
the general result known as Fermi's golden rule. The description has been
superseded by quantum electrodynamics, although the semi-classical version
continues to be more useful in most practical computations.

Origins
When the electrons in the atom are excited, for example by being heated, the
additional energy pushes the electrons to higher energy orbitals. When the
electrons fall back down and leave the excited state, energy is re-emitted in the
form of a photon. The wavelength (or equivalently, frequency) of the photon is
determined by the difference in energy between the two states. These emitted
photons form the element's spectrum.

The fact that only certain colors appear in an element's atomic emission spectrum
means that only certain frequencies of light are emitted. Each of these frequencies
are related to energy by the formula:
E
photon
=
h
ν
,
{\displaystyle E_{\text{photon}}=h\nu ,}where
E
photon
{\displaystyle E_{\text{photon}}} is the energy of the photon,
ν
{\displaystyle \nu } is its frequency, and
h
{\displaystyle h} is the Planck constant. This concludes that only photons with
specific energies are emitted by the atom. The principle of the atomic emission
spectrum explains the varied colors in neon signs, as well as chemical flame test
results (described below).

The frequencies of light that an atom can emit are dependent on states the
electrons can be in. When excited, an electron moves to a higher energy level or
orbital. When the electron falls back to its ground level the light is emitted.

Emission spectrum of hydrogen

The above picture shows the visible light emission spectrum for hydrogen. If only a
single atom of hydrogen were present, then only a single wavelength would be
observed at a given instant. Several of the possible emissions are observed because
the sample contains many hydrogen atoms that are in different initial energy states
and reach different final energy states. These different combinations lead to
simultaneous emissions at different wavelengths.

Emission spectrum of iron

Radiation from molecules
As well as the electronic transitions discussed above, the energy of a molecule can
also change via rotational, vibrational, and vibronic (combined vibrational and
electronic) transitions. These energy transitions often lead to closely spaced
groups of many different spectral lines, known as spectral bands. Unresolved band
spectra may appear as a spectral continuum.

Emission spectroscopy
Light consists of electromagnetic radiation of different wavelengths. Therefore,
when the elements or their compounds are heated either on a flame or by an electric
arc they emit energy in the form of light. Analysis of this light, with the help of
a spectroscope gives us a discontinuous spectrum. A spectroscope or a spectrometer
is an instrument which is used for separating the components of light, which have
different wavelengths. The spectrum appears in a series of lines called the line
spectrum. This line spectrum is called an atomic spectrum when it originates from
an atom in elemental form. Each element has a different atomic spectrum. The
production of line spectra by the atoms of an element indicate that an atom can
radiate only a certain amount of energy. This leads to the conclusion that bound
electrons cannot have just any amount of energy but only a certain amount of
energy.

The emission spectrum can be used to determine the composition of a material, since
it is different for each element of the periodic table. One example is astronomical
spectroscopy: identifying the composition of stars by analysing the received light.
The emission spectrum characteristics of some elements are plainly visible to the
naked eye when these elements are heated. For example, when platinum wire is dipped
into a sodium nitrate solution and then inserted into a flame, the sodium atoms
emit an amber yellow color. Similarly, when indium is inserted into a flame, the
flame becomes blue. These definite characteristics allow elements to be identified
by their atomic emission spectrum. Not all emitted lights are perceptible to the
naked eye, as the spectrum also includes ultraviolet rays and infrared radiation.
An emission spectrum is formed when an excited gas is viewed directly through a
spectroscope.

Schematic diagram of spontaneous emission

Emission spectroscopy is a spectroscopic technique which examines the wavelengths
of photons emitted by atoms or molecules during their transition from an excited
state to a lower energy state. Each element emits a characteristic set of discrete
wavelengths according to its electronic structure, and by observing these
wavelengths the elemental composition of the sample can be determined. Emission
spectroscopy developed in the late 19th century and efforts in theoretical
explanation of atomic emission spectra eventually led to quantum mechanics.

There are many ways in which atoms can be brought to an excited state. Interaction
with electromagnetic radiation is used in fluorescence spectroscopy, protons or
other heavier particles in particle-induced X-ray emission and electrons or X-ray
photons in energy-dispersive X-ray spectroscopy or X-ray fluorescence. The simplest
method is to heat the sample to a high temperature, after which the excitations are
produced by collisions between the sample atoms. This method is used in flame
emission spectroscopy, and it was also the method used by Anders Jonas Ångström
when he discovered the phenomenon of discrete emission lines in the 1850s.[1]

Although the emission lines are caused by a transition between quantized energy
states and may at first look very sharp, they do have a finite width, i.e. they are
composed of more than one wavelength of light. This spectral line broadening has
many different causes.

Emission spectroscopy is often referred to as optical emission spectroscopy because

of the light nature of what is being emitted.

Further information: Atomic emission spectroscopy

History
Further information: History of spectroscopy
In 1756 Thomas Melvill observed the emission of distinct patterns of colour when
salts were added to alcohol flames.[2] By 1785 James Gregory discovered the
principles of diffraction grating and American astronomer David Rittenhouse made
the first engineered diffraction grating.[3][4] In 1821 Joseph von Fraunhofer
solidified this significant experimental leap of replacing a prism as the source of
wavelength dispersion improving the spectral resolution and allowing for the
dispersed wavelengths to be quantified.[5]

In 1835, Charles Wheatstone reported that different metals could be distinguished

by bright lines in the emission spectra of their sparks, thereby introducing an
alternative to flame spectroscopy.[6][7] In 1849, J. B. L. Foucault experimentally
demonstrated that absorption and emission lines at the same wavelength are both due
to the same material, with the difference between the two originating from the
temperature of the light source.[8][9] In 1853, the Swedish physicist Anders Jonas
Ångström presented observations and theories about gas spectra.[10] Ångström
postulated that an incandescent gas emits luminous rays of the same wavelength as
those it can absorb. At the same time George Stokes and William Thomson (Kelvin)
were discussing similar postulates.[8] Ångström also measured the emission spectrum
from hydrogen later labeled the Balmer lines.[11][12] In 1854 and 1855, David Alter
published observations on the spectra of metals and gases, including an independent
observation of the Balmer lines of hydrogen.[13][14]
By 1859, Gustav Kirchhoff and Robert Bunsen noticed that several Fraunhofer lines
(lines in the solar spectrum) coincide with characteristic emission lines
identified in the spectra of heated elements.[15][16] It was correctly deduced that
dark lines in the solar spectrum are caused by absorption by chemical elements in
the solar atmosphere.[17]

Experimental technique in flame emission spectroscopy

The solution containing the relevant substance to be analysed is drawn into the
burner and dispersed into the flame as a fine spray. The solvent evaporates first,
leaving finely divided solid particles which move to the hottest region of the
flame where gaseous atoms and ions are produced through the dissociation of
molecules. Here electrons are excited as described above, and the spontaneously
emit photon to decay to lower energy states. It is common for a monochromator to be
used to allow for easy detection.

On a simple level, flame emission spectroscopy can be observed using just a flame
and samples of metal salts. This method of qualitative analysis is called a flame
test. For example, sodium salts placed in the flame will glow yellow from sodium
ions, while strontium (used in road flares) ions color it red. Copper wire will
create a blue colored flame, however in the presence of chloride gives green
(molecular contribution by CuCl).

Emission coefficient
Emission coefficient is a coefficient in the power output per unit time of an
electromagnetic source, a calculated value in physics. The emission coefficient of
a gas varies with the wavelength of the light. It has unit m⋅s−3⋅sr−1.[18] It is
also used as a measure of environmental emissions (by mass) per MW⋅h of electricity
generated, see: Emission factor.

Scattering of light
In Thomson scattering a charged particle emits radiation under incident light. The
particle may be an ordinary atomic electron, so emission coefficients have
practical applications.

If X dV dΩ dλ is the energy scattered by a volume element dV into solid angle dΩ

between wavelengths λ and λ + dλ per unit time then the emission coefficient is X.

The values of X in Thomson scattering can be predicted from incident flux, the
density of the charged particles and their Thomson differential cross section
(area/solid angle).

Spontaneous emission
A warm body emitting photons has a monochromatic emission coefficient relating to
its temperature and total power radiation. This is sometimes called the second
Einstein coefficient, and can be deduced from quantum mechanical theory.

See also
Absorption spectroscopy
Absorption spectrum
Atomic spectral line
Electromagnetic spectroscopy
Electromagnetic spectrum
Gas-discharge lamp, Table of emission spectra of gas discharge lamps
Isomeric shift
Isotopic shift
Luminous coefficient
Plasma physics
Rydberg formula
Spectral theory
The Diode equation includes the emission coefficient (which is not related to the
one discussed here)
Thermionic emission
References
Incorporated, SynLube. "Spectroscopy Oil Analysis". www.synlube.com. Retrieved
2017-02-24.
Melvill, Thomas (1756). "Observations on light and colours". Essays and
Observations, Physical and Literary. Read Before a Society in Edinburgh. 2: 12–
90. ; see pp. 33–36.
See:
Frauhofer. Jos. (1821) "Neue Modifikation des Lichtes durch gegenseitige Einwirkung
und Beugung der Strahlen, und Gesetze derselben" (New modification of light by the
mutual influence and the diffraction of [light] rays, and the laws thereof),
Denkschriften der Königlichen Akademie der Wissenschaften zu München (Memoirs of
the Royal Academy of Science in Munich), 8: 3–76.
Fraunhofer, Jos. (1823) "Kurzer Bericht von den Resultaten neuerer Versuche über
die Gesetze des Lichtes, und die Theorie derselben" (Short account of the results
of new experiments on the laws of light, and the theory thereof) Annalen der
Physik, 74(8): 337–378.
Parker AR (March 2005). "A geological history of reflecting optics". Journal of
the Royal Society, Interface. 2 (2): 1–17. doi:10.1098/rsif.2004.0026. PMC 1578258.
PMID 16849159.
OpenStax Astronomy, "Spectroscopy in Astronomy". OpenStax CNX. Sep 29, 2016
http://cnx.org/contents/1f92a120-370a-4547-b14e-a3df3ce6f083@3 Open access icon
Brian Bowers (2001). Sir Charles Wheatstone FRS: 1802-1875 (2nd ed.). IET. pp.
207–208. ISBN 978-0-85296-103-2.
Wheatstone (1836). "On the prismatic decomposition of electrical light". Report of
the Fifth Meeting of the British Association for the Advancement of Science; Held
at Dublin in 1835. Notices and Abstracts of Communications to the British
Association for the Advancement of Science, at the Dublin Meeting, August 1835.
London, England: John Murray. pp. 11–12.
Brand, pp. 60–62
See:
Foucault, L. (1849). "Lumière électrique" [Electric light]. Société Philomatique de
Paris. Extraits des Procès-Verbaux de Séances. (in French). 13: 16–20.
Foucault, L. (7 February 1849). "Lumière électrique" [Electric light]. L'Institut,
Journal Universel des Sciences (in French). 17 (788): 44–46.
See:
Ångström, A.J. (1852). "Optiska undersökningar" [Optical investigations]. Kongliga
Vetenskaps-Akademiens Handlingar [Proceedings of the Royal Academy of Science] (in
Swedish). 40: 333–360.
Ångström, A.J. (1855a). "Optische Untersuchungen" [Optical investigations]. Annalen
der Physik und Chemie (in German). 94: 141–165.
Ångström, A.J. (1855b). "Optical researches". Philosophical Magazine. 4th series.
9: 327–342. doi:10.1080/14786445508641880.
Wagner, H. J. (2005). "Early Spectroscopy and the Balmer Lines of Hydrogen".
Journal of Chemical Education. 82 (3): 380. Bibcode:2005JChEd..82..380W.
doi:10.1021/ed082p380.1.
(Ångström, 1852), p. 352; (Ångström, 1855b), p. 337.
Retcofsky, H. L. (2003). "Spectrum Analysis Discoverer?". Journal of Chemical
Education. 80 (9): 1003. Bibcode:2003JChEd..80.1003R. doi:10.1021/ed080p1003.1.
See:
Alter, David (1854). "On certain physical properties of light, produced by the
combustion of different metals, in the electric spark, refracted by a prism". The
American Journal of Science and Arts. 2nd series. 18: 55–57.
Alter, D. (1855). "On certain physical properties of the light of the electric
spark, within certain gases, as seen through a prism". The American Journal of
Science and Arts. 2nd series. 19: 213–214. Alter's observations of hydrogen's
optical spectrum appear on p. 213.
See:
Gustav Kirchhoff (1859) "Ueber die Fraunhofer'schen Linien" (On Fraunhofer's
lines), Monatsbericht der Königlichen Preussische Akademie der Wissenschaften zu
Berlin (Monthly report of the Royal Prussian Academy of Sciences in Berlin), 662–
665.
Gustav Kirchhoff (1859) "Ueber das Sonnenspektrum" (On the sun's spectrum),
Verhandlungen des naturhistorisch-medizinischen Vereins zu Heidelberg (Proceedings
of the Natural History / Medical Association in Heidelberg), 1 (7) : 251–255.
G. Kirchhoff (1860). "Ueber die Fraunhofer'schen Linien". Annalen der Physik. 185
(1): 148–150. Bibcode:1860AnP...185..148K. doi:10.1002/andp.18601850115.
G. Kirchhoff (1860). "Ueber das Verhältniss zwischen dem Emissionsvermögen und dem
Absorptionsvermögen der Körper für Wärme und Licht". Annalen der Physik. 185 (2):
275–301. Bibcode:1860AnP...185..275K. doi:10.1002/andp.18601850205.
Carroll, Bradley W. (2007). An Introduction to Modern Astrophysics. CA, USA:
Pearson Education. p. 256. ISBN 978-0-8053-0402-2.
External links
Emission spectra of atmospheric gases
NIST Physical Reference Data—Atomic Spectroscopy Databases
Color Simulation of Element Emission Spectrum Based on NIST data
Hydrogen emission spectrum
vte
Spectroscopy
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FT-IRRamanResonance RamanRotationalRotational–vibrationalVibrationalVibrational
circular dichroismNuclear resonance vibrational spectroscopyVibrational
spectroscopy of linear moleculesThermal infrared spectroscopy
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enhanced multiphoton ionization (REMPI)Raman Coherent anti-StokesRaman optical
activityLaser-induced breakdownAtomic emission Glow-discharge
opticalabsorptionCavity ring-down spectroscopySaturated absorption spectroscopy
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