Absorption spectroscopy refers to

spectroscopic Spectroscopy is the field of study that measures and interprets the electromagnetic spectra that result from the interaction between electromagnetic radiation and matter as a function of the wavelength or frequency of the radiation. Matter wa ...

techniques that measure the absorption of radiation, as a function of

frequency Frequency is the number of occurrences of a repeating event per unit of time. It is also occasionally referred to as ''temporal frequency'' for clarity, and is distinct from ''angular frequency''. Frequency is measured in hertz (Hz) which is eq ...

wavelength In physics, the wavelength is the spatial period of a periodic wave—the distance over which the wave's shape repeats. It is the distance between consecutive corresponding points of the same phase on the wave, such as two adjacent crests, t ...

, 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 The electromagnetic spectrum is the range of frequencies (the spectrum) of electromagnetic radiation and their respective wavelengths and photon energies. The electromagnetic spectrum covers electromagnetic waves with frequencies ranging fro ...

. Absorption spectroscopy is employed as an

analytical chemistry Analytical chemistry studies and uses instruments and methods to separate, identify, and quantify matter. In practice, separation, identification or quantification may constitute the entire analysis or be combined with another method. Separati ...

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 Infrared (IR), sometimes called infrared light, is electromagnetic radiation (EMR) with wavelengths longer than those of visible light. It is therefore invisible to the human eye. IR is generally understood to encompass wavelengths from around ...

and

ultraviolet–visible spectroscopy UV spectroscopy or UV–visible spectrophotometry (UV–Vis or UV/Vis) refers to absorption spectroscopy or reflectance spectroscopy in part of the ultraviolet and the full, adjacent visible regions of the electromagnetic spectrum. Being relative ...

are particularly common in analytical applications. Absorption spectroscopy is also employed in studies of molecular and atomic physics, astronomical spectroscopy and remote sensing. There is 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. Following are the major types of absorption spectroscopy:

Absorption spectrum

A material's absorption spectrum is the fraction of incident radiation absorbed by the material over a range of frequencies of Electromagnetic Radiation. The absorption spectrum is primarily determined by the

atom Every atom is composed of a nucleus and one or more electrons bound to the nucleus. The nucleus is made of one or more protons and a number of neutrons. Only the most common variety of hydrogen has no neutrons. Every solid, liquid, gas, ...

ic and molecular composition of the material. Radiation is more likely to be absorbed at frequencies that match the energy difference between two quantum mechanical states of the molecules. The absorption that occurs due to a transition between two states is referred to as an absorption line and a spectrum is typically composed of many lines. The frequencies where absorption lines occur, as well as their relative intensities, primarily depend on the

electronic Electronic may refer to: *Electronics, the science of how to control electric energy in semiconductor * ''Electronics'' (magazine), a defunct American trade journal *Electronic storage, the storage of data using an electronic device *Electronic co ...

and

molecular structure Molecular geometry is the three-dimensional arrangement of the atoms that constitute a molecule. It includes the general shape of the molecule as well as bond lengths, bond angles, torsional angles and any other geometrical parameters that deter ...

of the sample. The frequencies will also depend on the interactions between molecules in the sample, the

crystal structure In crystallography, crystal structure is a description of the ordered arrangement of atoms, ions or molecules in a crystalline material. Ordered structures occur from the intrinsic nature of the constituent particles to form symmetric patterns ...

in solids, and on several environmental factors (e.g.,

temperature Temperature is a physical quantity that expresses quantitatively the perceptions of hotness and coldness. Temperature is measurement, measured with a thermometer. Thermometers are calibrated in various Conversion of units of temperature, temp ...

pressure Pressure (symbol: ''p'' or ''P'') is the force applied perpendicular to the surface of an object per unit area over which that force is distributed. Gauge pressure (also spelled ''gage'' pressure)The preferred spelling varies by country and e ...

, electromagnetic field). The lines will also have a

width Length is a measure of distance. In the International System of Quantities, length is a quantity with dimension distance. In most systems of measurement a base unit for length is chosen, from which all other units are derived. In the Intern ...

and

shape A shape or figure is a graphical representation of an object or its external boundary, outline, or external surface, as opposed to other properties such as color, texture, or material type. A plane shape or plane figure is constrained to lie ...

that are primarily determined by the

spectral density The power spectrum S_(f) of a time series x(t) describes the distribution of power into frequency components composing that signal. According to Fourier analysis, any physical signal can be decomposed into a number of discrete frequencies, ...

or the

density of states In solid state physics and condensed matter physics, the density of states (DOS) of a system describes the number of modes per unit frequency range. The density of states is defined as D(E) = N(E)/V , where N(E)\delta E is the number of states i ...

of the system.

Theory

Absorption lines are typically classified by the nature of the quantum mechanical change induced in the molecule or atom. Rotational lines, for instance, occur when the rotational state of a molecule is changed. Rotational lines are typically found in the microwave spectral region. Vibrational lines correspond to changes in the vibrational state of the molecule and are typically found in the infrared region. Electronic lines correspond to a change in the electronic state of an atom or molecule and are typically found in the visible and ultraviolet region. X-ray absorptions are associated with the excitation of inner shell electrons in atoms. These changes can also be combined (e.g. rotation-vibration transitions), leading to new absorption lines at the combined energy of the two changes. The energy associated with the quantum mechanical change primarily determines the frequency of the absorption line but the frequency can be shifted by several types of interactions. Electric and magnetic fields can cause a shift. Interactions with neighboring molecules can cause shifts. For instance, absorption lines of the gas phase molecule can shift significantly when that molecule is in a liquid or solid phase and interacting more strongly with neighboring molecules. The width and shape of absorption lines are determined by the instrument used for the observation, the material absorbing the radiation and the physical environment of that material. It is common for lines to have the shape of a

Gaussian Carl Friedrich Gauss (1777–1855) is the eponym of all of the topics listed below. There are over 100 topics all named after this German mathematician and scientist, all in the fields of mathematics, physics, and astronomy. The English eponymo ...

or Lorentzian distribution. It is also common for a line to be described solely by its intensity and

instead of the entire shape being characterized. The integrated intensity—obtained by integrating the area under the absorption line—is proportional to the amount of the absorbing substance present. The intensity is also related to the temperature of the substance and the quantum mechanical interaction between the radiation and the absorber. This interaction is quantified by the transition moment and depends on the particular lower state the transition starts from, and the upper state it is connected to. The width of absorption lines may be determined by the

spectrometer 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 ...

used to record it. A spectrometer has an inherent limit on how narrow a line it can resolve and so the observed width may be at this limit. If the width is larger than the resolution limit, then it is primarily determined by the environment of the absorber. A liquid or solid absorber, in which neighboring molecules strongly interact with one another, tends to have broader absorption lines than a gas. Increasing the temperature or pressure of the absorbing material will also tend to increase the line width. It is also common for several neighboring transitions to be close enough to one another that their lines overlap and the resulting overall line is therefore broader yet.

Relation to transmission spectrum

Absorption and transmission spectra represent equivalent information and one can be calculated from the other through a mathematical transformation. A transmission spectrum will have its maximum intensities at wavelengths where the absorption is weakest because more light is transmitted through the sample. An absorption spectrum will have its maximum intensities at wavelengths where the absorption is strongest.

Relation to emission spectrum

Emission is a process by which a substance releases energy in the form of electromagnetic radiation. Emission can occur at any frequency at which absorption can occur, and this allows the absorption lines to be determined from an emission spectrum. The emission spectrum will typically have a quite different intensity pattern from the absorption spectrum, though, so the two are not equivalent. The absorption spectrum can be calculated from the emission spectrum using Einstein coefficients.

Relation to scattering and reflection spectra

The scattering and reflection spectra of a material are influenced by both its index of refraction and its absorption spectrum. In an optical context, the absorption spectrum is typically quantified by the extinction coefficient, and the extinction and index coefficients are quantitatively related through the Kramers-Kronig relation. Therefore, the absorption spectrum can be derived from a scattering or reflection spectrum. This typically requires simplifying assumptions or models, and so the derived absorption spectrum is an approximation.

Applications

Absorption spectroscopy is useful in chemical analysis because of its specificity and its quantitative nature. The specificity of absorption spectra allows compounds to be distinguished from one another in a mixture, making absorption spectroscopy useful in wide variety of applications. For instance, Infrared gas analyzers can be used to identify the presence of pollutants in the air, distinguishing the pollutant from nitrogen, oxygen, water and other expected constituents. The specificity also allows unknown samples to be identified by comparing a measured spectrum with a library of reference spectra. In many cases, it is possible to determine qualitative information about a sample even if it is not in a library. Infrared spectra, for instance, have characteristics absorption bands that indicate if carbon-hydrogen or carbon-oxygen bonds are present. An absorption spectrum can be quantitatively related to the amount of material present using the

Beer–Lambert law The Beer–Lambert law, also known as Beer's law, the Lambert–Beer law, or the Beer–Lambert–Bouguer law relates the attenuation of light to the properties of the material through which the light is travelling. The law is commonly applied t ...

. Determining the absolute concentration of a compound requires knowledge of the compound's

absorption coefficient The linear attenuation coefficient, attenuation coefficient, or narrow-beam attenuation coefficient characterizes how easily a volume of material can be penetrated by a beam of light, sound, particles, or other energy or matter. A coefficient valu ...

. The absorption coefficient for some compounds is available from reference sources, and it can also be determined by measuring the spectrum of a calibration standard with a known concentration of the target.

Remote sensing

One of the unique advantages of spectroscopy as an analytical technique is that measurements can be made without bringing the instrument and sample into contact. Radiation that travels between a sample and an instrument will contain the spectral information, so the measurement can be made remotely. Remote spectral sensing is valuable in many situations. For example, measurements can be made in toxic or hazardous environments without placing an operator or instrument at risk. Also, sample material does not have to be brought into contact with the instrument—preventing possible cross contamination. Remote spectral measurements present several challenges compared to laboratory measurements. The space in between the sample of interest and the instrument may also have spectral absorptions. These absorptions can mask or confound the absorption spectrum of the sample. These background interferences may also vary over time. The source of radiation in remote measurements is often an environmental source, such as sunlight or the thermal radiation from a warm object, and this makes it necessary to distinguish spectral absorption from changes in the source spectrum. To simplify these challenges,

Differential optical absorption spectroscopy In atmospheric chemistry, differential optical absorption spectroscopy (DOAS) is used to measure concentrations of trace gases. When combined with basic optical spectrometers such as prisms or diffraction gratings and automated, ground-based observa ...

has gained some popularity, as it focusses on differential absorption features and omits broad-band absorption such as aerosol extinction and extinction due to rayleigh scattering. This method is applied to ground-based, air-borne and satellite based measurements. Some ground-based methods provide the possibility to retrieve tropospheric and stratospheric trace gas profiles.

Astronomy

Astronomical spectroscopy Astronomical spectroscopy is the study of astronomy using the techniques of spectroscopy to measure the spectrum of electromagnetic radiation, including visible light, ultraviolet, X-ray, infrared and radio waves that radiate from stars a ...

is a particularly significant type of remote spectral sensing. In this case, the objects and samples of interest are so distant from earth that electromagnetic radiation is the only means available to measure them. Astronomical spectra contain both absorption and emission spectral information. Absorption spectroscopy has been particularly important for understanding interstellar clouds and determining that some of them contain molecules. Absorption spectroscopy is also employed in the study of

extrasolar planets An exoplanet or extrasolar planet is a planet outside the Solar System. The first possible evidence of an exoplanet was noted in 1917 but was not recognized as such. The first confirmation of detection occurred in 1992. A different planet, init ...

. Detection of extrasolar planets by the

transit method Any planet is an extremely faint light source compared to its parent star. For example, a star like the Sun is about a billion times as bright as the reflected light from any of the planets orbiting it. In addition to the intrinsic difficulty o ...

also measures their absorption spectrum and allows for the determination of the planet's atmospheric composition, temperature, pressure, and

scale height In atmospheric, earth, and planetary sciences, a scale height, usually denoted by the capital letter ''H'', is a distance ( vertical or radial) over which a physical quantity decreases by a factor of e (the base of natural logarithms, approxima ...

, and hence allows also for the determination of the planet's mass.

Atomic and molecular physics

Theoretical models, principally

quantum mechanical Quantum mechanics is a fundamental theory in physics that provides a description of the physical properties of nature at the scale of atoms and subatomic particles. It is the foundation of all quantum physics including quantum chemistry, qua ...

models, allow for the absorption spectra of atoms and molecules to be related to other physical properties such as

electronic structure In quantum chemistry, electronic structure is the state of motion of electrons in an electrostatic field created by stationary nuclei. The term encompasses both the wave functions of the electrons and the energies associated with them. Electr ...

, atomic or

molecular mass The molecular mass (''m'') is the mass of a given molecule: it is measured in daltons (Da or u). Different molecules of the same compound may have different molecular masses because they contain different isotopes of an element. The related quanti ...

, and

molecular geometry Molecular geometry is the three-dimensional arrangement of the atoms that constitute a molecule. It includes the general shape of the molecule as well as bond lengths, bond angles, torsional angles and any other geometrical parameters that dete ...

. Therefore, measurements of the absorption spectrum are used to determine these other properties.

Microwave spectroscopy Microwave spectroscopy is the spectroscopy method that employs microwaves, i.e. electromagnetic radiation at GHz frequencies, for the study of matter. History The ammonia molecule NH3 is shaped like a pyramid 0.38 Å in height, with an equilatera ...

, for example, allows for the determination of bond lengths and angles with high precision. In addition, spectral measurements can be used to determine the accuracy of theoretical predictions. For example, the

Lamb shift In physics, the Lamb shift, named after Willis Lamb, is a difference in energy between two energy levels 2''S''1/2 and 2''P''1/2 (in term symbol notation) of the hydrogen atom which was not predicted by the Dirac equation, according to which th ...

measured in the

hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic ...

atomic absorption spectrum was not expected to exist at the time it was measured. Its discovery spurred and guided the development of

quantum electrodynamics In particle physics, quantum electrodynamics (QED) is the relativistic quantum field theory of electrodynamics. In essence, it describes how light and matter interact and is the first theory where full agreement between quantum mechanics and spec ...

, and measurements of the Lamb shift are now used to determine the

fine-structure constant In physics, the fine-structure constant, also known as the Sommerfeld constant, commonly denoted by (the Greek letter ''alpha''), is a fundamental physical constant which quantifies the strength of the electromagnetic interaction between el ...

Experimental methods

Basic approach

The most straightforward approach to absorption spectroscopy is to generate radiation with a source, measure a reference spectrum of that radiation with a

detector A sensor is a device that produces an output signal for the purpose of sensing a physical phenomenon. In the broadest definition, a sensor is a device, module, machine, or subsystem that detects events or changes in its environment and sends ...

and then re-measure the sample spectrum after placing the material of interest in between the source and detector. The two measured spectra can then be combined to determine the material's absorption spectrum. The sample spectrum alone is not sufficient to determine the absorption spectrum because it will be affected by the experimental conditions—the spectrum of the source, the absorption spectra of other materials in between the source and detector and the wavelength dependent characteristics of the detector. The reference spectrum will be affected in the same way, though, by these experimental conditions and therefore the combination yields the absorption spectrum of the material alone. A wide variety of radiation sources are employed in order to cover the electromagnetic spectrum. For spectroscopy, it is generally desirable for a source to cover a broad swath of wavelengths in order to measure a broad region of the absorption spectrum. Some sources inherently emit a broad spectrum. Examples of these include

globar A Globar is used as thermal light source for infrared spectroscopy. The preffered material for making Globar is silicon carbide that is shaped as rods or arches of various sizes. When inserted into a circuit that provides it with electric current, ...

s or other

black body A black body or blackbody is an idealized physical body that absorbs all incident electromagnetic radiation, regardless of frequency or angle of incidence. The name "black body" is given because it absorbs all colors of light. A black body ...

sources in the infrared,

mercury lamp A mercury-vapor lamp is a gas-discharge lamp that uses an electric arc through vaporized Mercury (element), mercury to produce light. The arc discharge is generally confined to a small fused quartz arc tube mounted within a larger Soda–lime g ...

s in the visible and ultraviolet and

x-ray tube An X-ray tube is a vacuum tube that converts electrical input power into X-rays. The availability of this controllable source of X-rays created the field of radiography, the imaging of partly opaque objects with penetrating radiation. In contrast ...

s. One recently developed, novel source of broad spectrum radiation is synchrotron radiation which covers all of these spectral regions. Other radiation sources generate a narrow spectrum but the emission wavelength can be tuned to cover a spectral range. Examples of these include

klystron A klystron is a specialized linear-beam vacuum tube, invented in 1937 by American electrical engineers Russell and Sigurd Varian,Pond, Norman H. "The Tube Guys". Russ Cochran, 2008 p.31-40 which is used as an amplifier for high radio frequen ...

s in the microwave region and

laser A laser is a device that emits light through a process of optical amplification based on the stimulated emission of electromagnetic radiation. The word "laser" is an acronym for "light amplification by stimulated emission of radiation". The fi ...

s across the infrared, visible and ultraviolet region (though not all lasers have tunable wavelengths). The detector employed to measure the radiation power will also depend on the wavelength range of interest. Most detectors are sensitive to a fairly broad spectral range and the sensor selected will often depend more on the sensitivity and noise requirements of a given measurement. Examples of detectors common in spectroscopy include

heterodyne receiver A superheterodyne receiver, often shortened to superhet, is a type of radio receiver that uses frequency mixing to convert a received signal to a fixed intermediate frequency (IF) which can be more conveniently processed than the original car ...

s in the microwave,

bolometer A bolometer is a device for measuring radiant heat by means of a material having a temperature-dependent electrical resistance. It was invented in 1878 by the American astronomer Samuel Pierpont Langley. Principle of operation A bolometer ...

s in the millimeter-wave and infrared,

mercury cadmium telluride Hg1−xCdxTe or mercury cadmium telluride (also cadmium mercury telluride, MCT, MerCad Telluride, MerCadTel, MerCaT or CMT) is a chemical compound of cadmium telluride (CdTe) and mercury telluride (HgTe) with a tunable bandgap spanning the shortwav ...

and other cooled

semiconductor A semiconductor is a material which has an electrical conductivity value falling between that of a conductor, such as copper, and an insulator, such as glass. Its resistivity falls as its temperature rises; metals behave in the opposite way. ...

detectors in the infrared, and photodiodes and photomultiplier tubes in the visible and ultraviolet. If both the source and the detector cover a broad spectral region, then it is also necessary to introduce a means of resolving the wavelength of the radiation in order to determine the spectrum. Often a spectrograph is used to spatially separate the wavelengths of radiation so that the power at each wavelength can be measured independently. It is also common to employ interferometry to determine the spectrum— Fourier transform infrared spectroscopy is a widely used implementation of this technique. Two other issues that must be considered in setting up an absorption spectroscopy experiment include the

optics Optics is the branch of physics that studies the behaviour and properties of light, including its interactions with matter and the construction of instruments that use or detect it. Optics usually describes the behaviour of visible, ultrav ...

used to direct the radiation and the means of holding or containing the sample material (called a

cuvette A cuvette (French: cuvette = "little vessel") is a small tube-like container with straight sides and a circular or square cross section. It is sealed at one end, and made of a clear, transparent material such as plastic, glass, or fused quartz. ...

or cell). For most UV, visible, and NIR measurements the use of precision quartz cuvettes are necessary. In both cases, it is important to select materials that have relatively little absorption of their own in the wavelength range of interest. The absorption of other materials could interfere with or mask the absorption from the sample. For instance, in several wavelength ranges it is necessary to measure the sample under

vacuum A vacuum is a space devoid of matter. The word is derived from the Latin adjective ''vacuus'' for "vacant" or " void". An approximation to such vacuum is a region with a gaseous pressure much less than atmospheric pressure. Physicists often di ...

or in a rare gas environment because gases in the atmosphere have interfering absorption features.

Specific approaches

* Cavity ring down spectroscopy (CRDS) *

Laser absorption spectrometry Laser absorption spectrometry (LAS) refers to techniques that use lasers to assess the concentration or amount of a species in gas phase by absorption spectrometry (AS). Optical spectroscopic techniques in general, and laser-based techniques in ...

(LAS) *

Mössbauer spectroscopy Mössbauer spectroscopy is a spectroscopic technique based on the Mössbauer effect. This effect, discovered by Rudolf Mössbauer (sometimes written "Moessbauer", German: "Mößbauer") in 1958, consists of the nearly recoil-free emission and abs ...

Photoacoustic spectroscopy Photoacoustic spectroscopy is the measurement of the effect of absorbed electromagnetic energy (particularly of light) on matter by means of acoustic detection. The discovery of the photoacoustic effect dates to 1880 when Alexander Graham Bell sh ...

Photoemission spectroscopy Photoemission spectroscopy (PES), also known as photoelectron spectroscopy, refers to energy measurement of electrons emitted from solids, gases or liquids by the photoelectric effect, in order to determine the binding energies of electrons in th ...

Photothermal optical microscopy Photothermal optical microscopy / "photothermal single particle microscopy" is a technique that is based on detection of non-fluorescent labels. It relies on absorption properties of labels ( gold nanoparticles, semiconductor nanocrystals, etc.), a ...

* Photothermal spectroscopy * Reflectance spectroscopy *

Tunable diode laser absorption spectroscopy Tunable diode laser absorption spectroscopy (TDLAS, sometimes referred to as TDLS, TLS or TLAS) is a technique for measuring the concentration of certain species such as methane, water vapor and many more, in a gaseous mixture using tunable diode l ...

(TDLAS) *

X-ray absorption fine structure X-ray absorption fine structure (XAFS) is a specific structure observed in X-ray absorption spectroscopy (XAS). By analyzing the XAFS, information can be acquired on the local structure and on the unoccupied local electronic states. Atomic spectr ...

(XAFS) *X-ray absorption near edge structure (

XANES X-ray absorption near edge structure (XANES), also known as near edge X-ray absorption fine structure (NEXAFS), is a type of absorption spectroscopy that indicates the features in the X-ray absorption spectra ( XAS) of condensed matter due to the ...

) *

Total absorption spectroscopy Total absorption spectroscopy is a measurement technique that allows the measurement of the gamma radiation emitted in the different nuclear gamma transitions that may take place in the daughter nucleus after its unstable parent has decayed by mean ...

(TAS) * Reflection-absorption infrared spectroscopy (RAIRS)

References

External links

Solar absorption spectrum

WEBB Space Telescope, Part 3 of a series: Spectroscopy 101 – Types of Spectra and Spectroscopy

Visible Absorption Spectrum Simulation

Plot Absorption Intensity for many molecules in HITRAN database
{{DEFAULTSORT:Absorption Spectroscopy Scientific techniques Analytical chemistry Spectroscopy Electromagnetic radiation Astrochemistry Radiation