X-ray

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 fi ...

(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 Synchrotron radiation (also known as magnetobremsstrahlung radiation) is the electromagnetic radiation emitted when relativistic charged particles are subject to an acceleration perpendicular to their velocity (). It is produced artificially in ...

facilities, which provide intense and tunable

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 ...

beams. Samples can be in the gas phase, solutions, or solids.

Background

XAS data is obtained by tuning the

photon A photon () is an elementary particle that is a quantum of the electromagnetic field, including electromagnetic radiation such as light and radio waves, and the force carrier for the electromagnetic force. Photons are massless, so they always ...

energy, using a crystalline monochromator, to a range where

core electron Core electrons are the electrons in an atom that are not valence electrons and do not participate in chemical bonding. The nucleus and the core electrons of an atom form the atomic core. Core electrons are tightly bound to the nucleus. Therefore, un ...

s can be excited (0.1-100 keV). The edges are, in part, named by which core electron is excited: the

principal quantum number In quantum mechanics, the principal quantum number (symbolized ''n'') is one of four quantum numbers assigned to each electron in an atom to describe that electron's state. Its values are natural numbers (from 1) making it a discrete variable. A ...

s n = 1, 2, and 3, correspond to the K-, L-, and M-edges, respectively. For instance, excitation of a 1s electron occurs at the

K-edge In X-ray absorption spectroscopy, the K-edge is a sudden increase in x-ray absorption occurring when the energy of the X-rays is just above the binding energy of the innermost electron shell of the atoms interacting with the photons. The term is ba ...

, while excitation of a 2s or 2p electron occurs at an L-edge (Figure 1). There are three main regions found on a spectrum generated by XAS data which are then thought of as separate spectroscopic techniques (Figure 2): # The ''absorption threshold'' determined by the transition to the lowest unoccupied states: # The 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 ...

), introduced in 1980 and later in 1983 and also called NEXAFS (near-edge X-ray absorption fine structure), which are dominated by core transitions to quasi bound states (multiple scattering resonances) for photoelectrons with kinetic energy in the range from 10 to 150 eV above the chemical potential, called "shape resonances" in molecular spectra since they are due to final states of short life-time degenerate with the continuum with the Fano line-shape. In this range multi-electron excitations and many-body final states in strongly correlated systems are relevant; # In the high kinetic energy range of the photoelectron, the scattering cross-section with neighbor atoms is weak, and the absorption spectra are dominated by

EXAFS Extended X-ray absorption fine structure (EXAFS), along with X-ray absorption near edge structure (XANES), is a subset of X-ray absorption spectroscopy ( XAS). Like other absorption spectroscopies, XAS techniques follow Beer's law. The X-ray ...

(extended X-ray absorption fine structure), where the scattering of the ejected

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 ...

of neighboring atoms can be approximated by single scattering events. In 1985, it was shown that multiple scattering theory can be used to interpret both

and

; therefore, the experimental analysis focusing on both regions is now called

XAFS 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 ...

. XAS is a type of

from a core initial state with a well defined symmetry; therefore, the quantum mechanical

selection rules In physics and chemistry, a selection rule, or transition rule, formally constrains the possible transitions of a system from one quantum state to another. Selection rules have been derived for electromagnetic transitions in molecules, in atoms, in ...

select the symmetry of the final states in the continuum, which are usually a mixture of multiple components. The most intense features are due to electric-dipole allowed transitions (i.e. ''Δℓ'' = ± 1) to unoccupied final states. For example, the most intense features of a K-edge are due to core transitions from 1s → p-like final states, while the most intense features of the L₃-edge are due to 2p → d-like final states. XAS methodology can be broadly divided into four experimental categories that can give complementary results to each other: metal K-edge,

metal L-edge Metal L-edge spectroscopy is a spectroscopic technique used to study the electronic structures of transition metal atoms and complexes. This method measures X-ray absorption caused by the excitation of a metal 2p electron to unfilled d orbital ...

ligand K-edge In X-ray absorption spectroscopy, the K-edge is a sudden increase in x-ray absorption occurring when the energy of the X-rays is just above the binding energy of the innermost electron shell of the atoms interacting with the photons. The term is ba ...

, and EXAFS. The most obvious means of mapping heterogeneous samples beyond x‐ray absorption contrast is through elemental analysis by x‐ray fluorescence, akin to EDX methods in electron microscopy.

Applications

XAS is a technique used in different scientific fields including

molecular A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bioche ...

and

condensed matter physics Condensed matter physics is the field of physics that deals with the macroscopic and microscopic physical properties of matter, especially the solid and liquid phases which arise from electromagnetic forces between atoms. More generally, the sub ...

,Rawat, Pankaj Singh, R. C. Srivastava, Gagan Dixit, and K. Asokan. "Structural, functional and magnetic ordering modifications in graphene oxide and graphite by 100 MeV gold ion irradiation." Vacuum 182 (2020): 109700.https://doi.org/10.1016/j.vacuum.2020.109700 materials science and engineering,

chemistry Chemistry is the science, scientific study of the properties and behavior of matter. It is a natural science that covers the Chemical element, elements that make up matter to the chemical compound, compounds made of atoms, molecules and ions ...

earth science Earth science or geoscience includes all fields of natural science related to the planet Earth. This is a branch of science dealing with the physical, chemical, and biological complex constitutions and synergistic linkages of Earth's four spheres ...

, and

biology Biology is the scientific study of life. It is a natural science with a broad scope but has several unifying themes that tie it together as a single, coherent field. For instance, all organisms are made up of cells that process hereditary i ...

. In particular, its unique sensitivity to the local structure, as compared to

x-ray diffraction X-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles ...

, have been exploited for studying: *

Amorphous solid 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'' ("wit ...

s 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

ion implantation Ion implantation is a low-temperature process by which ions of one element are accelerated into a solid target, thereby changing the physical, chemical, or electrical properties of the target. Ion implantation is used in semiconductor device fab ...

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 lattices 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_ ...

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 *

Catalysis Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...

* Vibrational dynamics *

Ion 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 conve ...

s in

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 of elements *

Liquid water Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as a s ...

and aqueous solutions * Used to detect bone fracture * Used to determine the concentration of any liquid in any tank

References

External links

* * {{cite web , vauthors = Newville M , date = 25 July 2008 , title = Fundamentals of XAFS , url = https://docs.xrayabsorption.org/tutorials/XAFS_Fundamentals.pdf , publisher = University of Chicago , location = Chicago, IL Materials science Environmental chemistry Synchrotron-related techniques Absorb

Background

Applications

See also

References

External links