A spectral line is a weaker or stronger region in an otherwise uniform and continuous spectrum. It may result 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 ones of atoms [1] and molecules, [2] 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) [3] 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 the energy will be spontaneously re-emitted, either as one photon at the same frequency as the original one 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 cooler 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, perhaps in the presence of a broad spectrum from a cooler source. The intensity of light, over a narrow frequency range, is increased due to emission by the hot material.
Spectral lines are highly atom-specific, and can be used to identify the chemical composition of any medium. Several elements, including helium, thallium, and caesium, were discovered by spectroscopic means. Spectral lines also depend on the temperature and density of the material, so they are widely used to determine the physical conditions of stars and other celestial bodies that cannot be analyzed by other means.
Depending on the material and its physical conditions, the energy of the involved photons can vary widely, with the spectral lines observed across the electromagnetic spectrum, from radio waves to gamma rays.
Strong spectral lines in the visible part of the electromagnetic spectrum often have a unique Fraunhofer line designation, such as K for a line at 393.366 nm emerging from singly-ionized calcium atom, 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:
Cu II— copper ion with +1 charge, Cu1+
Fe III— iron ion with +2 charge, Fe2+
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 tiny spectral band with a nonzero range of frequencies, not a single frequency (i.e., a nonzero spectral width). 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. Some authors use the term "radiative broadening" to refer specifically to the part of natural broadening caused by the spontaneous radiative decay. [4] 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. [5]
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.
Opacity broadening is an example of a non-local broadening mechanism. 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 (this effect usually referred to as rotational broadening). The greater the rate of rotation, the broader the line. Another example is an imploding plasma shell in a Z-pinch.
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.
Atomic absorption spectroscopy (AAS) and atomic emission spectroscopy (AES) is a spectroanalytical procedure for the quantitative determination of chemical elements by free atoms in the gaseous state. Atomic absorption spectroscopy is based on absorption of light by free metallic ions.
The electromagnetic spectrum is the full range of electromagnetic radiation, organized by frequency or wavelength. The spectrum is divided into separate bands, with different names for the electromagnetic waves within each band. From low to high frequency these are: radio waves, microwaves, infrared, visible light, ultraviolet, X-rays, and gamma rays. The electromagnetic waves in each of these bands have different characteristics, such as how they are produced, how they interact with matter, and their practical applications.
Spectroscopy is the field of study that measures and interprets electromagnetic spectra. In narrower contexts, spectroscopy is the precise study of color as generalized from visible light to all bands of the electromagnetic spectrum.
Stimulated emission is the process by which an incoming photon of a specific frequency can interact with an excited atomic electron, causing it to drop to a lower energy level. The liberated energy transfers to the electromagnetic field, creating a new photon with a frequency, polarization, and direction of travel that are all identical to the photons of the incident wave. This is in contrast to spontaneous emission, which occurs at a characteristic rate for each of the atoms/oscillators in the upper energy state regardless of the external electromagnetic field.
Atomic, molecular, and optical physics (AMO) is the study of matter–matter and light–matter interactions, at the scale of one or a few atoms and energy scales around several electron volts. The three areas are closely interrelated. AMO theory includes classical, semi-classical and quantum treatments. Typically, the theory and applications of emission, absorption, scattering of electromagnetic radiation (light) from excited atoms and molecules, analysis of spectroscopy, generation of lasers and masers, and the optical properties of matter in general, fall into these categories.
The interstellar medium (ISM) is the matter and radiation that exists 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. Although the density of atoms in the ISM is usually far below that in the best laboratory vacuums, the mean free path between collisions is short compared to typical interstellar lengths, so on these scales the ISM behaves as a gas, responding to pressure forces, and not as a collection of non-interacting particles.
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 emitted by the thermal motion of particles in matter. Thermal radiation transmits as an electromagnetic wave through both matter and vacuum. When matter absorbs thermal radiation its temperature will tend to rise. All matter with a temperature greater than absolute zero emits thermal radiation. The emission of energy arises from a combination of electronic, molecular, and lattice oscillations in a material. Kinetic energy is converted to electromagnetism due to charge-acceleration or dipole oscillation. At room temperature, most of the emission is in the infrared (IR) spectrum. Thermal radiation is one of the fundamental mechanisms of heat transfer, along with conduction and convection.
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.
Absorption spectroscopy is spectroscopy that involves techniques that measure the absorption of electromagnetic 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.
In quantum mechanics, an absorption band is a range of wavelengths, frequencies or energies in the electromagnetic spectrum that are characteristic of a particular transition from initial to final state in a substance.
In atomic, molecular, and optical physics, the Einstein coefficients are quantities describing the probability of absorption or emission of a photon 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. Throughout this article, "light" refers to any electromagnetic radiation, not necessarily in the visible spectrum.
In atomic physics, Doppler broadening is 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 emission (absorption) line broadening. This resulting line profile is known as a Doppler profile.
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.
In physics, the Ives–Stilwell experiment tested the contribution of relativistic time dilation to the Doppler shift of light. The result was in agreement with the formula for the transverse Doppler effect and was the first direct, quantitative confirmation of the time dilation factor. Since then many Ives–Stilwell type experiments have been performed with increased precision. Together with the Michelson–Morley and Kennedy–Thorndike experiments it forms one of the fundamental tests of special relativity theory. Other tests confirming the relativistic Doppler effect are the Mössbauer rotor experiment and modern Ives–Stilwell experiments.
Lyman continuum photons, shortened to Ly continuum photons or Lyc photons, are the photons emitted from stars or active galactic nuclei 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.
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.