Extended X-ray absorption fine structure (EXAFS), along with 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 p ...

), is a subset of X-ray absorption spectroscopy (

XAS X-ray absorption spectroscopy (XAS) is a widely used technique for determining the local geometric and/or electronic structure of matter. The experiment is usually performed at synchrotron radiation facilities, which provide intense and tunabl ...

). Like other absorption spectroscopies, XAS techniques follow Beer's law. The

X-ray An X-ray, or, much less commonly, X-radiation, is a penetrating form of high-energy electromagnetic radiation. Most X-rays have a wavelength ranging from 10 picometers to 10 nanometers, corresponding to frequencies in the range 30&nb ...

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 ...

of a material as a function of energy is obtained using X-rays of a narrow energy resolution are directed at a sample and the incident and transmitted x-ray intensity is recorded as the incident x-ray energy is incremented. When the incident x-ray energy matches the

binding energy In physics and chemistry, binding energy is the smallest amount of energy required to remove a particle from a system of particles or to disassemble a system of particles into individual parts. In the former meaning the term is predominantly use ...

of an

electron The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family, and are generally thought to be elementary particles because they have no kn ...

of an atom within the sample, the number of x-rays absorbed by the sample increases dramatically, causing a drop in the transmitted x-ray intensity. This results in an absorption edge. Every element has a set of unique absorption edges corresponding to different binding energies of its electrons, giving XAS element selectivity. XAS spectra are most often collected at

synchrotron A synchrotron is a particular type of cyclic particle accelerator, descended from the cyclotron, in which the accelerating particle beam travels around a fixed closed-loop path. The magnetic field which bends the particle beam into its closed p ...

s because of the high intensity of synchrotron X-ray sources allow the concentration of the absorbing element to reach as low as a few parts per million. Absorption would be undetectable if the source is too weak. Because X-rays are highly penetrating, XAS samples can be gases, solids or liquids.

Background

EXAFS spectra are displayed as plots of the absorption coefficient of a given material versus

energy In physics, energy (from Ancient Greek: ἐνέργεια, ''enérgeia'', “activity”) is the quantitative property that is transferred to a body or to a physical system, recognizable in the performance of work and in the form of heat a ...

, typically in a 500 – 1000 eV range beginning before an

absorption edge An absorption edge, absorption discontinuity or absorption limit is a sharp discontinuity in the absorption spectrum of a substance. These discontinuities occur at wavelengths where the energy of an absorbed photon corresponds to an electronic tran ...

of an element in the sample. The x-ray absorption coefficient is usually normalized to unit step height. This is done by regressing a line to the region before and after the absorption edge, subtracting the pre-edge line from the entire data set and dividing by the absorption step height, which is determined by the difference between the pre-edge and post-edge lines at the value of E0 (on the absorption edge). The normalized absorption spectra are often called

spectra. These spectra can be used to determine the average oxidation state of the element in the sample. The XANES spectra are also sensitive to the coordination environment of the absorbing atom in the sample. Finger printing methods have been used to match the XANES spectra of an unknown sample to those of known "standards". Linear combination fitting of several different standard spectra can give an estimate to the amount of each of the known standard spectra within an unknown sample. X-ray absorption spectra are produced over the range of 200 – 35,000 eV. The dominant physical process is one where the absorbed photon ejects a core

photoelectron The photoelectric effect is the emission of electrons when electromagnetic radiation, such as light, hits a material. Electrons emitted in this manner are called photoelectrons. The phenomenon is studied in condensed matter physics, and solid sta ...

from the absorbing atom, leaving behind a core hole. The atom with the core hole is now excited. The ejected photoelectron's energy will be equal to that of the absorbed photon minus the

of the initial core state. The ejected photoelectron interacts with electrons in the surrounding non-excited atoms. If the ejected photoelectron is taken to have a

wave In physics, mathematics, and related fields, a wave is a propagating dynamic disturbance (change from equilibrium) of one or more quantities. Waves can be periodic, in which case those quantities oscillate repeatedly about an equilibrium (res ...

-like nature and the surrounding atoms are described as point scatterers, it is possible to imagine the

backscatter In physics, backscatter (or backscattering) is the reflection of waves, particles, or signals back to the direction from which they came. It is usually a diffuse reflection due to scattering, as opposed to specular reflection as from a mirror, a ...

ed electron waves interfering with the forward-propagating waves. The resulting interference pattern shows up as a

modulation In electronics and telecommunications, modulation is the process of varying one or more properties of a periodic waveform, called the ''carrier signal'', with a separate signal called the ''modulation signal'' that typically contains informatio ...

of the measured absorption coefficient, thereby causing the oscillation in the EXAFS spectra. A simplified plane-wave single-scattering theory has been used for interpretation of EXAFS spectra for many years, although modern methods (like FEFF, GNXAS) have shown that curved-wave corrections and multiple-scattering effects can not be neglected. The photelectron scattering amplitude in the low energy range (5-200 eV) of the photoelectron kinetic energy become much larger so that multiple scattering events become dominant in the

(or NEXAFS) spectra. The

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, tro ...

of the photoelectron is dependent on the energy and phase of the backscattered wave which exists at the central atom. The wavelength changes as a function of the energy of the incoming photon. The

phase Phase or phases may refer to: Science *State of matter, or phase, one of the distinct forms in which matter can exist *Phase (matter), a region of space throughout which all physical properties are essentially uniform * Phase space, a mathematic ...

and

amplitude The amplitude of a periodic variable is a measure of its change in a single period (such as time or spatial period). The amplitude of a non-periodic signal is its magnitude compared with a reference value. There are various definitions of amplit ...

of the backscattered wave are dependent on the type of atom doing the backscattering and the distance of the backscattering atom from the central atom. The dependence of the scattering on atomic species makes it possible to obtain information pertaining to the chemical coordination environment of the original absorbing (centrally excited) atom by analyzing these EXAFS data.

Experimental considerations

Since EXAFS requires a tunable x-ray source, data are frequently collected at

s, often at

beamline In accelerator physics, a beamline refers to the trajectory of the beam of particles, including the overall construction of the path segment (guide tubes, diagnostic devices) along a specific path of an accelerator facility. This part is either ...

s which are especially optimized for the purpose. The utility of a particular synchrotron to study a particular solid depends on the

brightness Brightness is an attribute of visual perception in which a source appears to be radiating or reflecting light. In other words, brightness is the perception elicited by the luminance of a visual target. The perception is not linear to luminance, ...

of the x-ray flux at the absorption edges of the relevant elements.

Applications

XAS is an interdisciplinary technique and its unique properties, as compared to x-ray diffraction, have been exploited for understanding the details of local structure in: *

glass Glass is a non-crystalline, often transparent, amorphous solid that has widespread practical, technological, and decorative use in, for example, window panes, tableware, and optics. Glass is most often formed by rapid cooling (quenching) of ...

amorphous In condensed matter physics and materials science, an amorphous solid (or non-crystalline solid, glassy solid) is a solid that lacks the long-range order that is characteristic of a crystal. Etymology The term comes from the Greek ''a'' ("wi ...

and

liquid A liquid is a nearly incompressible fluid that conforms to the shape of its container but retains a (nearly) constant volume independent of pressure. As such, it is one of the four fundamental states of matter (the others being solid, gas, a ...

systems *

solid solution A solid solution, a term popularly used for metals, is a homogenous mixture of two different kinds of atoms in solid state and have a single crystal structure. Many examples can be found in metallurgy, geology, and solid-state chemistry. The word ...

s * doping and ionic implantation of materials for

electronics The field of electronics is a branch of physics and electrical engineering that deals with the emission, behaviour and effects of electrons using electronic devices. Electronics uses active devices to control electron flow by amplification ...

* local distortions of

crystal lattice In geometry and crystallography, a Bravais lattice, named after , is an infinite array of discrete points generated by a set of discrete translation operations described in three dimensional space by : \mathbf = n_1 \mathbf_1 + n_2 \mathbf_2 + n ...

s *

organometallic compounds Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and so ...

metalloproteins Metalloprotein is a generic term for a protein that contains a metal ion cofactor. A large proportion of all proteins are part of this category. For instance, at least 1000 human proteins (out of ~20,000) contain zinc-binding protein domains al ...

* metal clusters * vibrational dynamics *

ions An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conven ...

solution Solution may refer to: * Solution (chemistry), a mixture where one substance is dissolved in another * Solution (equation), in mathematics ** Numerical solution, in numerical analysis, approximate solutions within specified error bounds * Soluti ...

s *

speciation Speciation is the evolutionary process by which populations evolve to become distinct species. The biologist Orator F. Cook coined the term in 1906 for cladogenesis, the splitting of lineages, as opposed to anagenesis, phyletic evolution within ...

of elements XAS provides complementary to diffraction information on peculiarities of local structural and thermal disorder in crystalline and multi-component materials. The use of atomistic simulations such as

molecular dynamics Molecular dynamics (MD) is a computer simulation method for analyzing the physical movements of atoms and molecules. The atoms and molecules are allowed to interact for a fixed period of time, giving a view of the dynamic "evolution" of the ...

or the

reverse Monte Carlo The Reverse Monte Carlo (RMC) modelling method is a variation of the standard Metropolis–Hastings algorithm to solve an inverse problem whereby a model is adjusted until its parameters have the greatest consistency with experimental data. Invers ...

method can help in extracting more reliable and richer structural information.

Examples

EXAFS is, like

, a highly sensitive technique with elemental specificity. As such, EXAFS is an extremely useful way to determine the chemical state of practically important species which occur in very low abundance or concentration. Frequent use of EXAFS occurs in

environmental chemistry Environmental chemistry is the scientific study of the chemical and biochemical phenomena that occur in natural places. It should not be confused with green chemistry, which seeks to reduce potential pollution at its source. It can be defined as t ...

, where scientists try to understand the propagation of

pollutant A pollutant or novel entity is a substance or energy introduced into the environment that has undesired effects, or adversely affects the usefulness of a resource. These can be both naturally forming (i.e. minerals or extracted compounds like oi ...

s through an

ecosystem An ecosystem (or ecological system) consists of all the organisms and the physical environment with which they interact. These biotic and abiotic components are linked together through nutrient cycles and energy flows. Energy enters the syste ...

. EXAFS can be used along with

accelerator mass spectrometry Accelerator mass spectrometry (AMS) is a form of mass spectrometry that accelerates ions to extraordinarily high kinetic energies before mass analysis. The special strength of AMS among the mass spectrometric methods is its power to separate a r ...

forensic Forensic science, also known as criminalistics, is the application of science to Criminal law, criminal and Civil law (legal system), civil laws, mainly—on the criminal side—during criminal investigation, as governed by the legal standard ...

examinations, particularly in

nuclear Nuclear may refer to: Physics Relating to the nucleus of the atom: * Nuclear engineering *Nuclear physics *Nuclear power *Nuclear reactor *Nuclear weapon *Nuclear medicine *Radiation therapy *Nuclear warfare Mathematics *Nuclear space *Nuclear ...

non-proliferation Nuclear proliferation is the spread of nuclear weapons, fissionable material, and weapons-applicable nuclear technology and information to nations not recognized as " Nuclear Weapon States" by the Treaty on the Non-Proliferation of Nuclear Wea ...

applications.

History

A very detailed, balanced and informative account about the history of EXAFS (originally called Kossel's structures) is given by R. Stumm von Bordwehr. A more modern and accurate account of the history of XAFS (EXAFS and XANES) is given by the leader of the group that developed the modern version of EXAFS in an award lecture by Edward A. Stern.

References

Bibliography

Books

* * * *

Book chapters

Papers

* * * * * F.W. Lytle
"The EXAFS family tree: a personal history of the development of extended X-ray absorption fine structure"
* * A. Kodre, I. Arčon, Proceedings of 36th International Conference on Microelectronics, Devices and Materials, MIDEM, Postojna, Slovenia, October 28-20, (2000), p. 191-196

External links

International X-ray Absorption SocietyFEFF Project, University of Washington, Seattle

GNXAS project and XAS laboratory, Università di CamerinoEXAFS Spectroscopy Laboratory (Riga, Latvia)Community web site for XAFS
{{Branches of Spectroscopy X-ray absorption spectroscopy