Emission spectrum

The emission spectrum of a chemical element or chemical compound is the spectrum of frequencies of electromagnetic radiation emitted due to an atom or molecule making a transition from a high energy state to a lower energy state. The photon energy of the emitted photon 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 the elements in matter of unknown composition. Similarly, the emission spectra of molecules can be used in chemical analysis of substances.

MHL
Emission spectrum of a metal halide lamp.
Cmglee Cambridge Science Festival 2016 sodium lines
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

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:

,

where is the energy of the photon, is its frequency, and is Planck's 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-H
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-Fe
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 strontium nitrate solution and then inserted into a flame, the strontium atoms emit a red color. Similarly, when copper is inserted into a flame, the flame becomes green. 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 lighting. An emission is formed when an excited gas is viewed directly through a spectroscope.

AtomicLineSpEm
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.

History

Emission lines from hot gases were first discovered by Ångström, and the technique was further developed by David Alter, Gustav Kirchhoff and Robert Bunsen.

See the history of spectroscopy for details.

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. Here electrons are excited as described above. 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 units of ms−3sr−1.[2] It is also used as a measure of environmental emissions (by mass) per MWh 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

References

  1. ^ Incorporated, SynLube. "Spectroscopy Oil Analysis". www.synlube.com. Retrieved 2017-02-24.
  2. ^ Carroll, Bradley W. (2007). An Introduction to Modern Astrophysics. CA, USA: Pearson Education. p. 256. ISBN 0-8053-0402-9.

External links

Absorption spectroscopy

Absorption spectroscopy refers to spectroscopic techniques that measure the absorption of radiation, as a function of frequency or wavelength, due to its interaction with a sample. The sample absorbs energy, i.e., photons, from the radiating field. The intensity of the absorption varies as a function of frequency, and this variation is the absorption spectrum. Absorption spectroscopy is performed across the electromagnetic spectrum.

Absorption spectroscopy is employed as an analytical chemistry tool to determine the presence of a particular substance in a sample and, in many cases, to quantify the amount of the substance present. Infrared and ultraviolet-visible spectroscopy are particularly common in analytical applications. Absorption spectroscopy is also employed in studies of molecular and atomic physics, astronomical spectroscopy and remote sensing.

There are a wide range of experimental approaches for measuring absorption spectra. The most common arrangement is to direct a generated beam of radiation at a sample and detect the intensity of the radiation that passes through it. The transmitted energy can be used to calculate the absorption. The source, sample arrangement and detection technique vary significantly depending on the frequency range and the purpose of the experiment.

Asteroid spectral types

An asteroid spectral type is assigned to asteroids based on their emission spectrum, color, and sometimes albedo. These types are thought to correspond to an asteroid's surface composition. For small bodies that are not internally differentiated, the surface and internal compositions are presumably similar, while large bodies such as Ceres and Vesta are known to have internal structure. Over the years, there has been a number of surveys that resulted in a set of different taxonomic systems such as the Tholen, SMASS and Bus–DeMeo classification.

Bathochromic shift

Bathochromic shift (from Greek βαθύς bathys, "deep"; and χρῶμα chrōma, "color"; hence less common alternate spelling "bathychromic") is a change of spectral band position in the absorption, reflectance, transmittance, or emission spectrum of a molecule to a longer wavelength (lower frequency). Because the red color in the visible spectrum has a longer wavelength than most other colors, the effect is also commonly called a red shift.

Hypsochromic shift is a change to shorter wavelength (higher frequency)

Cornell box

The Cornell box is a test aimed at determining the accuracy of rendering software by comparing the rendered scene with an actual photograph of the same scene, and has become a commonly used 3D test model. It was created by Cindy M. Goral, Kenneth E. Torrance, Donald P. Greenberg, and Bennett Battaile at the Cornell University Program of Computer Graphics for their paper Modeling the Interaction of Light Between Diffuse Surfaces published and presented at SIGGRAPH'84.A physical model of the box is created and photographed with a CCD camera. The exact settings are then measured from the scene: emission spectrum of the light source, reflectance spectra of all the surfaces, exact position and size of all objects, walls, light source and camera.

The same scene is then reproduced in the renderer, and the output file is compared with the photograph.

The basic environment consists of:

One light source in the center of a white ceiling

A green right wall

A red left wall

A white back wall

A white floorObjects are often placed inside the box. The first objects placed inside the environment were two white boxes. Another common version first used to test photon mapping includes two spheres: one with a perfect mirror surface and one made of glass.

The physical properties of the box are designed to show diffuse interreflection. For example, some light should reflect off the red and green walls and bounce onto the white walls, so parts of the white walls should appear slightly red or green.

Today, the Cornell box is often used to demonstrate renderers in a similar way as the Stanford bunny and the Utah teapot are; computer scientists often use the scene just for its visual properties without comparing it to test data from a physical model.

Discrete spectrum

A physical quantity is said to have a discrete spectrum if it takes only distinct values, with gaps between one value and the next.

The classical example of discrete spectrum (for which the term was first used) is the characteristic set of discrete spectral lines seen in the emission spectrum and absorption spectrum of isolated atoms of a chemical element, which only absorb and emit light at particular wavelengths. The technique of spectroscopy is based on this phenomenon.

Discrete spectra are contrasted with the continuous spectra also seen in such experiments, for example in thermal emission, in synchrotron radiation, and many other light-producing phenomena.

Discrete spectra are seen in many other phenomena, such as vibrating strings, microwaves in a metal cavity, sound waves in a pulsating star, and resonances in high-energy particle physics.

The general phenomenon of discrete spectra in physical systems can be mathematically modeled with tools of functional analysis, specifically by the decomposition of the spectrum of a linear operator acting on a functional space.

Energy-dispersive X-ray spectroscopy

Energy-dispersive X-ray spectroscopy (EDS, EDX, EDXS or XEDS), sometimes called energy dispersive X-ray analysis (EDXA) or energy dispersive X-ray microanalysis (EDXMA), is an analytical technique used for the elemental analysis or chemical characterization of a sample. It relies on an interaction of some source of X-ray excitation and a sample. Its characterization capabilities are due in large part to the fundamental principle that each element has a unique atomic structure allowing a unique set of peaks on its electromagnetic emission spectrum (which is the main principle of spectroscopy).

To stimulate the emission of characteristic X-rays from a specimen, a high-energy beam of charged particles such as electrons or protons (see PIXE), or a beam of X-rays, is focused into the sample being studied. At rest, an atom within the sample contains ground state (or unexcited) electrons in discrete energy levels or electron shells bound to the nucleus. The incident beam may excite an electron in an inner shell, ejecting it from the shell while creating an electron hole where the electron was. An electron from an outer, higher-energy shell then fills the hole, and the difference in energy between the higher-energy shell and the lower energy shell may be released in the form of an X-ray. The number and energy of the X-rays emitted from a specimen can be measured by an energy-dispersive spectrometer. As the energies of the X-rays are characteristic of the difference in energy between the two shells and of the atomic structure of the emitting element, EDS allows the elemental composition of the specimen to be measured.

Flame test

A flame test is an analytic procedure used in chemistry to detect the presence of certain elements, primarily metal ions, based on each element's characteristic emission spectrum. The color of flames in general also depends on temperature; see flame color.

Fluorescein isothiocyanate

Fluorescein isothiocyanate (FITC) is a derivative of fluorescein used in wide-ranging applications including flow cytometry. First described in 1942, FITC is the original fluorescein molecule functionalized with an isothiocyanate reactive group (-N=C=S), replacing a hydrogen atom on the bottom ring of the structure. It is typically available as a mixture of isomers, fluorescein 5-isothiocyanate (5-FITC) and fluorescein 6-isothiocyanate (6-FITC). FITC is reactive towards nucleophiles including amine and sulfhydryl groups on proteins.

A succinimidyl-ester functional group attached to the fluorescein core, creating "NHS-fluorescein", forms another common amine reactive derivative that has much greater specificity toward primary amines in the presence of other nucleophiles.

FITC has excitation and emission spectrum peak wavelengths of approximately 495 nm/519 nm, giving it a green color. Like most fluorochromes, it is prone to photobleaching. Because of the problem with photobleaching, derivatives of fluorescein such as Alexa 488 and DyLight 488 have been tailored for various chemical and biological applications where greater photostability, higher fluorescence intensity, or different attachment groups are needed.

Fluorescence spectroscopy

Fluorescence spectroscopy (also known as fluorimetry or spectrofluorometry) is a type of electromagnetic spectroscopy that analyzes fluorescence from a sample. It involves using a beam of light, usually ultraviolet light, that excites the electrons in molecules of certain compounds and causes them to emit light; typically, but not necessarily, visible light. A complementary technique is absorption spectroscopy. In the special case of single molecule fluorescence spectroscopy, intensity fluctuations from the emitted light are measured from either single fluorophores, or pairs of fluorophores.

Devices that measure fluorescence are called fluorometers.

Fluorometer

A fluorometer or fluorimeter is a device used to measure parameters of fluorescence: its intensity and wavelength distribution of emission spectrum after excitation by a certain spectrum of light. These parameters are used to identify the presence and the amount of specific molecules in a medium. Modern fluorometers are capable of detecting fluorescent molecule concentrations as low as 1 part per trillion.

Fluorescence analysis can be orders of magnitude more sensitive than other techniques. Applications include chemistry/biochemistry, medicine, environmental monitoring. For instance, they are used to measure chlorophyll fluorescence to investigate plant physiology.

Fourier-transform spectroscopy

Fourier-transform spectroscopy is a measurement technique whereby spectra are collected based on measurements of the coherence of a radiative source, using time-domain or space-domain measurements of the electromagnetic radiation or other type of radiation. It can be applied to a variety of types of spectroscopy including optical spectroscopy, infrared spectroscopy (FTIR, FT-NIRS), nuclear magnetic resonance (NMR) and magnetic resonance spectroscopic imaging (MRSI), mass spectrometry and electron spin resonance spectroscopy. There are several methods for measuring the temporal coherence of the light (see: field-autocorrelation), including the continuous wave Michelson or Fourier-transform spectrometer and the pulsed Fourier-transform spectrograph (which is more sensitive and has a much shorter sampling time than conventional spectroscopic techniques, but is only applicable in a laboratory environment).

The term Fourier-transform spectroscopy reflects the fact that in all these techniques, a Fourier transform is required to turn the raw data into the actual spectrum, and in many of the cases in optics involving interferometers, is based on the Wiener–Khinchin theorem.

GY Andromedae

GY Andromedae (GY And) is an α2 Canum Venaticorum type variable star in the northern constellation Andromeda. Its brightness fluctuates in visual magnitude between 6.27m and 6.41m, making it a challenge to view with the naked eye even in good seeing conditions. The magnetic activity on this star shows an unusually long period of variability, cycling about once every 23 years. Based upon parallax measurements, this star is located at a distance of about 520 light-years (160 parsecs) from the Earth.This is classified as an Ap/Bp star, with a peculiar spectrum showing lines of chromium and europium that change in intensity over a period matching the variability cycle, although opposite in phase. Its most striking characteristic is the presence of the unstable element promethium in its emission spectrum. All isotopes of this element are radioactive with half lives of 17.7 years or less. The promethium in the outer envelope may be generated by the spontaneous fission of higher mass transuranic elements.

Homogeneous broadening

Homogeneous broadening is a type of emission spectrum broadening in which all atoms radiating from a specific level under consideration radiate with equal opportunity. If an optical emitter (e.g. an atom) shows homogeneous broadening, its spectral linewidth is its natural linewidth, with a Lorentzian profile.

Hydrogen spectral series

The emission spectrum of atomic hydrogen has been divided into a number of spectral series, with wavelengths given by the Rydberg formula. These observed spectral lines are due to the electron making transitions between two energy levels in an atom. The classification of the series by the Rydberg formula was important in the development of quantum mechanics. The spectral series are important in astronomical spectroscopy for detecting the presence of hydrogen and calculating red shifts.

IAEDANS

IAEDANS is an organic fluorophore (fluorescent molecule). It stands for 5-({2-[(iodoacetyl)amino]ethyl}amino)naphthalene-1-sulfonic acid. It is widely used as a marker in fluorescence spectroscopy.

1,5-IAEDANS has a peak excitation wavelength of 336 nm and a peak emission wavelength of 490 nm. The extinction coefficient of the dye is 5700. It is soluble in dimethylformamide (DMF) or buffer above pH 6 and reacts primarily with thiols.

The absorption spectrum IAEDANS overlaps well with the emission spectrum of tryptophan, making it useful as an acceptor in FRET experiments. It can also be used as a resonance energy donor to fluorophores such as fluorescein, Alexa Fluor 488, Oregon Green, and BODIPY FL.

Laser dye

Laser dyes are large organic molecules with molecular weights of a few hundred mu. When one of these organic molecules is dissolved in a suitable liquid solvent (such as ethanol, methanol, or an ethanol-water mixture) it can be used as laser medium in a dye laser. Laser dye solutions absorb at shorter wavelengths and emit at longer wavelengths. Successful laser dyes include the coumarins and the rhodamines. Coumarin dyes emit in the green region of the spectrum while rhodamine dyes are used for emission in the yellow-red. The color emitted by the laser dyes depend upon the surrounding medium i.e.the medium in which they are dissolved. However, there are dozens of laser dyes that can be used to span continuously the emission spectrum from the near ultraviolet to the near infrared.Laser dyes are also used to dope solid-state matrices, such as poly(methyl methacrylate) (PMMA), and ORMOSILs, to provide gain media for solid state dye lasers.

Planck postulate

The Planck postulate (or Planck's postulate), one of the fundamental principles of quantum mechanics, is the postulate that the energy of oscillators in a black body is quantized, and is given by

,

where is an integer (1, 2, 3, ...), is Planck's constant, and (the Greek letter nu, not the Latin letter v) is the frequency of the oscillator.

The postulate was introduced by Max Planck in his derivation of his law of black body radiation in 1900. This assumption allowed Planck to derive a formula for the entire spectrum of the radiation emitted by a black body. Planck was unable to justify this assumption based on classical physics; he considered quantization as being purely a mathematical trick, rather than (as is now known) a fundamental change in the understanding of the world. In other words, Planck then contemplated virtual oscillators.

In 1905, Albert Einstein adapted the Planck postulate to explain the photoelectric effect, but Einstein proposed that the energy of photons themselves was quantized, and that quantization was not merely a feature of microscopic oscillators. Planck's postulate was further applied to understanding the Compton effect, and was applied by Niels Bohr to explain the emission spectrum of the hydrogen atom and derive the correct value of the Rydberg constant.

Spectroscopy

Spectroscopy is the study of the interaction between matter and electromagnetic radiation. Historically, spectroscopy originated through the study of visible light dispersed according to its wavelength, by a prism. Later the concept was expanded greatly to include any interaction with radiative energy as a function of its wavelength or frequency, predominantly in the electromagnetic spectrum, though matter waves and acoustic waves can also be considered forms of radiative energy; recently, with tremendous difficulty, even gravitational waves have been associated with a spectral signature in the context of LIGO and laser interferometry. Spectroscopic data are often represented by an emission spectrum, a plot of the response of interest as a function of wavelength or frequency.

Spectroscopy, primarily in the electromagnetic spectrum, is a fundamental exploratory tool in the fields of physics, chemistry, and astronomy, allowing the composition and structure of matter to be investigated at molecular scale, macro scale, and over astronomical distances. Important applications arise from biomedical spectroscopy in the areas of tissue analysis and medical imaging.

Sunlight

Sunlight is a portion of the electromagnetic radiation given off by the Sun, in particular infrared, visible, and ultraviolet light. On Earth, sunlight is filtered through Earth's atmosphere, and is obvious as daylight when the Sun is above the horizon. When the direct solar radiation is not blocked by clouds, it is experienced as sunshine, a combination of bright light and radiant heat. When it is blocked by clouds or reflects off other objects, it is experienced as diffused light. The World Meteorological Organization uses the term "sunshine duration" to mean the cumulative time during which an area receives direct irradiance from the Sun of at least 120 watts per square meter. Other sources indicate an "Average over the entire earth" of "164 Watts per square meter over a 24 hour day".The ultraviolet radiation in sunlight has both positive and negative health effects, as it is both a requisite for vitamin D3 synthesis and a mutagen.

Sunlight takes about 8.3 minutes to reach Earth from the surface of the Sun. A photon starting at the center of the Sun and changing direction every time it encounters a charged particle would take between 10,000 and 170,000 years to get to the surface.Sunlight is a key factor in photosynthesis, the process used by plants and other autotrophic organisms to convert light energy, normally from the Sun, into chemical energy that can be used to synthesize carbohydrates and to fuel the organisms' activities.

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