A spectral line is a dark or bright line in an otherwise uniform and continuous spectrum, resulting from emission or absorption of light in a narrow frequency range, compared with the nearby frequencies. Spectral lines are often used to identify atoms and molecules. These "fingerprints" can be compared to the previously collected "fingerprints" of atomsand molecules, and are thus used to identify the atomic and molecular components of stars and planets, which would otherwise be impossible.
Spectral lines are the result of interaction between a quantum system (usually atoms, but sometimes molecules or atomic nuclei) and a single photon. When a photon has about the right amount of energy (which is connected to its frequency) [ citation needed ]to allow a change in the energy state of the system (in the case of an atom this is usually an electron changing orbitals), the photon is absorbed. Then it will be spontaneously re-emitted, either in the same frequency as the original or in a cascade, where the sum of the energies of the photons emitted will be equal to the energy of the one absorbed (assuming the system returns to its original state).
A spectral line may be observed either as an emission line or an absorption line. Which type of line is observed depends on the type of material and its temperature relative to another emission source. An absorption line is produced when photons from a hot, broad spectrum source pass through a cold material. The intensity of light, over a narrow frequency range, is reduced due to absorption by the material and re-emission in random directions. By contrast, a bright emission line is produced when photons from a hot material are detected in the presence of a broad spectrum from a cold source. The intensity of light, over a narrow frequency range, is increased due to emission by the material.
Spectral lines are highly atom-specific, and can be used to identify the chemical composition of any medium capable of letting light pass through it. Several elements were discovered by spectroscopic means, including helium, thallium, and caesium. Spectral lines also depend on the physical conditions of the gas, so they are widely used to determine the chemical composition of stars and other celestial bodies that cannot be analyzed by other means, as well as their physical conditions.
Mechanisms other than atom-photon interaction can produce spectral lines. Depending on the exact physical interaction (with molecules, single particles, etc.), the frequency of the involved photons will vary widely, and lines can be observed across the electromagnetic spectrum, from radio waves to gamma rays.
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Strong spectral lines in the visible part of the spectrum often have a unique Fraunhofer line designation, such as K for a line at 393.366 nm emerging from singly-ionized Ca +, though some of the Fraunhofer "lines" are blends of multiple lines from several different species. In other cases, the lines are designated according to the level of ionization by adding a Roman numeral to the designation of the chemical element. Neutral atoms are denoted with the Roman numeral I, singly ionized atoms with II, and so on, so that, for example, Fe IX represents eight times ionized iron.
More detailed designations usually include the line wavelength and may include a multiplet number (for atomic lines) or band designation (for molecular lines). Many spectral lines of atomic hydrogen also have designations within their respective series, such as the Lyman series or Balmer series. Originally all spectral lines were classified into series: the Principal series, Sharp series , and Diffuse series . These series exist across atoms of all elements, and the patterns for all atoms are well-predicted by the Rydberg-Ritz formula. These series were later associated with suborbitals.
There are a number of effects which control spectral line shape. A spectral line extends over a range of frequencies, not a single frequency (i.e., it has a nonzero linewidth). In addition, its center may be shifted from its nominal central wavelength. There are several reasons for this broadening and shift. These reasons may be divided into two general categories – broadening due to local conditions and broadening due to extended conditions. Broadening due to local conditions is due to effects which hold in a small region around the emitting element, usually small enough to assure local thermodynamic equilibrium. Broadening due to extended conditions may result from changes to the spectral distribution of the radiation as it traverses its path to the observer. It also may result from the combining of radiation from a number of regions which are far from each other.
The lifetime of excited states results in natural broadening, also known as lifetime broadening. The uncertainty principle relates the lifetime of an excited state (due to spontaneous radiative decay or the Auger process) with the uncertainty of its energy. A short lifetime will have a large energy uncertainty and a broad emission. This broadening effect results in an unshifted Lorentzian profile. The natural broadening can be experimentally altered only to the extent that decay rates can be artificially suppressed or enhanced.
The atoms in a gas which are emitting radiation will have a distribution of velocities. Each photon emitted will be "red"- or "blue"-shifted by the Doppler effect depending on the velocity of the atom relative to the observer. The higher the temperature of the gas, the wider the distribution of velocities in the gas. Since the spectral line is a combination of all of the emitted radiation, the higher the temperature of the gas, the broader the spectral line emitted from that gas. This broadening effect is described by a Gaussian profile and there is no associated shift.
The presence of nearby particles will affect the radiation emitted by an individual particle. There are two limiting cases by which this occurs:
Pressure broadening may also be classified by the nature of the perturbing force as follows:
Inhomogeneous broadening is a general term for broadening because some emitting particles are in a different local environment from others, and therefore emit at a different frequency. This term is used especially for solids, where surfaces, grain boundaries, and stoichiometry variations can create a variety of local environments for a given atom to occupy. In liquids, the effects of inhomogeneous broadening is sometimes reduced by a process called motional narrowing .
Certain types of broadening are the result of conditions over a large region of space rather than simply upon conditions that are local to the emitting particle.
Electromagnetic radiation emitted at a particular point in space can be reabsorbed as it travels through space. This absorption depends on wavelength. The line is broadened because the photons at the line center have a greater reabsorption probability than the photons at the line wings. Indeed, the reabsorption near the line center may be so great as to cause a self reversal in which the intensity at the center of the line is less than in the wings. This process is also sometimes called self-absorption.
Radiation emitted by a moving source is subject to Doppler shift due to a finite line-of-sight velocity projection. If different parts of the emitting body have different velocities (along the line of sight), the resulting line will be broadened, with the line width proportional to the width of the velocity distribution. For example, radiation emitted from a distant rotating body, such as a star, will be broadened due to the line-of-sight variations in velocity on opposite sides of the star. The greater the rate of rotation, the broader the line. Another example is an imploding plasma shell in a Z-pinch.
Radiative broadening of the spectral absorption profile occurs because the on-resonance absorption in the center of the profile is saturated at much lower intensities than the off-resonant wings. Therefore, as intensity rises, absorption in the wings rises faster than absorption in the center, leading to a broadening of the profile. Radiative broadening occurs even at very low light intensities.
Each of these mechanisms can act in isolation or in combination with others. Assuming each effect is independent, the observed line profile is a convolution of the line profiles of each mechanism. For example, a combination of the thermal Doppler broadening and the impact pressure broadening yields a Voigt profile.
However, the different line broadening mechanisms are not always independent. For example, the collisional effects and the motional Doppler shifts can act in a coherent manner, resulting under some conditions even in a collisional narrowing, known as the Dicke effect.
The phrase "spectral lines", when not qualified, usually refers to lines having wavelengths in the visible band of the full electromagnetic spectrum. Many spectral lines occur at wavelengths outside this range. At shorter wavelengths, which correspond to higher energies, ultraviolet spectral lines include the Lyman series of hydrogen. At the much shorter wavelengths of X-rays, the lines are known as characteristic X-rays because they remain largely unchanged for a given chemical element, independent of their chemical environment. Longer wavelengths correspond to lower energies, where the infrared spectral lines include the Paschen series of hydrogen. At even longer wavelengths, the radio spectrum includes the 21-cm line used to detect neutral hydrogen throughout the cosmos.
For each element, the following table shows the spectral lines which appear in the visible spectrum at about 400-700 nm.
The electromagnetic spectrum is the range of frequencies of electromagnetic radiation and their respective wavelengths and photon energies.
Spectroscopy is the study of the interaction between matter and electromagnetic radiation as a function of the wavelength or frequency of the radiation. In simpler terms, spectroscopy is the precise study of color as generalized from visible light to all bands of the electromagnetic spectrum; indeed, historically, spectroscopy originated as the study of the wavelength dependence of the absorption by gas phase matter of visible light dispersed by a prism. Matter waves and acoustic waves can also be considered forms of radiative energy, and recently gravitational waves have been associated with a spectral signature in the context of the Laser Interferometer Gravitational-Wave Observatory (LIGO).
In astronomy, the interstellar medium (ISM) is the matter and radiation that exist in the space between the star systems in a galaxy. This matter includes gas in ionic, atomic, and molecular form, as well as dust and cosmic rays. It fills interstellar space and blends smoothly into the surrounding intergalactic space. The energy that occupies the same volume, in the form of electromagnetic radiation, is the interstellar radiation field.
X-ray fluorescence (XRF) is the emission of characteristic "secondary" X-rays from a material that has been excited by being bombarded with high-energy X-rays or gamma rays. The phenomenon is widely used for elemental analysis and chemical analysis, particularly in the investigation of metals, glass, ceramics and building materials, and for research in geochemistry, forensic science, archaeology and art objects such as paintings
Thermal radiation is electromagnetic radiation generated by the thermal motion of particles in matter. All matter with a temperature greater than absolute zero emits thermal radiation. Particle motion results in charge-acceleration or dipole oscillation which produces electromagnetic radiation.
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 elements in matter of unknown composition. Similarly, the emission spectra of molecules can be used in chemical analysis of substances.
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.
Plasma diagnostics are a pool of methods, instruments, and experimental techniques used to measure properties of a plasma, such as plasma components' density, distribution function over energy (temperature), their spatial profiles and dynamics, which enable to derive plasma parameters.
Atomic spectroscopy is the study of the electromagnetic radiation absorbed and emitted by atoms. Since unique elements have characteristic (signature) spectra, atomic spectroscopy, specifically the electromagnetic spectrum or mass spectrum, is applied for determination of elemental compositions. It can be divided by atomization source or by the type of spectroscopy used. In the latter case, the main division is between optical and mass spectrometry. Mass spectrometry generally gives significantly better analytical performance, but is also significantly more complex. This complexity translates into higher purchase costs, higher operational costs, more operator training, and a greater number of components that can potentially fail. Because optical spectroscopy is often less expensive and has performance adequate for many tasks, it is far more common Atomic absorption spectrometers are one of the most commonly sold and used analytical devices.
According to quantum mechanics, atoms and molecules can only hold certain defined quantities of energy, or exist in specific states. When such quanta of electromagnetic radiation are emitted or absorbed by an atom or molecule, energy of the radiation changes the state of the atom or molecule from an initial state to a final state. An absorption band is a range of wavelengths, frequencies or energies in the electromagnetic spectrum which are characteristic of a particular transition from initial to final state in a substance.
Einstein coefficients are mathematical quantities which are a measure of the probability of absorption or emission of light by an atom or molecule. The Einstein A coefficients are related to the rate of spontaneous emission of light, and the Einstein B coefficients are related to the absorption and stimulated emission of light.
In atomic physics, Doppler broadening is the broadening of spectral lines due to the Doppler effect caused by a distribution of velocities of atoms or molecules. Different velocities of the emitting particles result in different Doppler shifts, the cumulative effect of which is the line broadening. This resulting line profile is known as a Doppler profile. A particular case is the thermal Doppler broadening due to the thermal motion of the particles. Then, the broadening depends only on the frequency of the spectral line, the mass of the emitting particles, and their temperature, and therefore can be used for inferring the temperature of an emitting body.
Quantum mechanics is the study of very small things. It explains the behavior of matter and its interactions with energy on the scale of atomic and subatomic particles. By contrast, classical physics explains matter and energy only on a scale familiar to human experience, including the behavior of astronomical bodies such as the Moon. Classical physics is still used in much of modern science and technology. However, towards the end of the 19th century, scientists discovered phenomena in both the large (macro) and the small (micro) worlds that classical physics could not explain. The desire to resolve inconsistencies between observed phenomena and classical theory led to two major revolutions in physics that created a shift in the original scientific paradigm: the theory of relativity and the development of quantum mechanics. This article describes how physicists discovered the limitations of classical physics and developed the main concepts of the quantum theory that replaced it in the early decades of the 20th century. It describes these concepts in roughly the order in which they were first discovered. For a more complete history of the subject, see History of quantum mechanics.
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.
Lyman continuum photons, shortened to Ly continuum photons or Lyc photons, are the photons emitted from stars at photon energies above the Lyman limit. Hydrogen is ionized by absorbing LyC. Working from Victor Schumann's discovery of ultraviolet light, from 1906 to 1914, Theodore Lyman observed that atomic hydrogen absorbs light only at specific frequencies and the Lyman series is thus named after him. All the wavelengths in the Lyman series are in the ultraviolet band. This quantized absorption behavior occurs only up to an energy limit, known as the ionization energy. In the case of neutral atomic hydrogen, the minimum ionization energy is equal to the Lyman limit, where the photon has enough energy to completely ionize the atom, resulting in a free proton and a free electron. Above this energy, all wavelengths of light may be absorbed. This forms a continuum in the energy spectrum; the spectrum is continuous rather than composed of many discrete lines, which are seen at lower energies.
Atomic emission spectroscopy (AES) is a method of chemical analysis that uses the intensity of light emitted from a flame, plasma, arc, or spark at a particular wavelength to determine the quantity of an element in a sample. The wavelength of the atomic spectral line in the emission spectrum gives the identity of the element while the intensity of the emitted light is proportional to the number of atoms of the element. The sample may be excited by various methods.
Photoelectrochemical processes are processes in photoelectrochemistry; they usually involve transforming light into other forms of energy. These processes apply to photochemistry, optically pumped lasers, sensitized solar cells, luminescence, and photochromism.
In spectroscopy, the Dicke effect, also known as Dicke narrowing or sometimes collisional narrowing, named after Robert H. Dicke, refers to narrowing of the Doppler broadening of a spectral line due to collisions the emitting species experiences with other particles.
In astronomy and in astrophysics, for radiative losses of the solar corona, it is meant the energy flux radiated from the external atmosphere of the Sun, and, in particular, the processes of production of the radiation coming from the solar corona and transition region, where the plasma is optically-thin. On the contrary, in the chromosphere, where the temperature decreases from the photospheric value of 6000 K to the minimum of 4400 K, the optical depth is about 1, and the radiation is thermal.
A spectrometer is a scientific instrument used to separate and measure spectral components of a physical phenomenon. Spectrometer is a broad term often used to describe instruments that measure a continuous variable of a phenomenon where the spectral components are somehow mixed. In visible light a spectrometer can separate white light and measure individual narrow bands of color, called a spectrum. A mass spectrometer measures the spectrum of the masses of the atoms or molecules present in a gas. The first spectrometers were used to split light into an array of separate colors. Spectrometers were developed in early studies of physics, astronomy, and chemistry. The capability of spectroscopy to determine chemical composition drove its advancement and continues to be one of its primary uses. Spectrometers are used in astronomy to analyze the chemical composition of stars and planets, and spectrometers gather data on the origin of the universe.