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X-ray absorption spectroscopy

Nature Reviews Methods Primers volume 4, Article number: 89 (2024) Cite this article

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Abstract

X-ray absorption spectroscopy (XAS) is an established experimental technique for studying the electronic and local geometric structures of materials. As a short-range order structural probe, it can be applied to all states of matter: crystalline or amorphous solids, liquids and gases. The method is element selective and highly sensitive, with little compromise required to integrate complex sample environment set-ups. These characteristics make the technique suitable for applications in a range of scientific disciplines, from chemistry and catalysis to environmental science, materials science, physics, biology, medicine and cultural heritage. An XAS spectrum is obtained by measuring the modulation of the sample absorption coefficient as a function of the incident X-ray beam energy. Data are usually collected in transmission detection mode, although fluorescence and electron yield detection modes are often used. The XAS spectrum is divided into two regimes: X-ray absorption near-edge structure and extended X-ray absorption fine structure. In this Primer, an overview of XAS fundamentals is given, together with a description of the experimental set-ups, sample requirements, data analysis and possible applications.

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Fig. 1: Processes in X-ray absorption spectroscopy.
Fig. 2: Log–log plots of X-ray mass absorption coefficients versus photon energy.
Fig. 3: Schematic diagram of X-ray absorption fine structure measurements.
Fig. 4: Example normalization and extraction of an extended X-ray absorption fine structure spectrum from the raw X-ray absorption spectroscopy data.
Fig. 5: Data analysis of the extended X-ray absorption fine structure spectrum of the [NiCl(H2O5)]+ cluster.
Fig. 6: Example applications.

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Authors and Affiliations

  1. School of Physics, The University of Melbourne, Parkville, Victoria, Australia

    Christopher T. Chantler

  2. Department of Physics, Illinois Institute of Technology, Chicago, IL, USA

    Grant Bunker

  3. Department of Chemistry, University of Roma ‘La Sapienza’, Rome, Italy

    Paola D’Angelo

  4. Diamond Light Source, Didcot, UK

    Sofia Diaz-Moreno

Authors
  1. Christopher T. Chantler
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  2. Grant Bunker
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  3. Paola D’Angelo
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  4. Sofia Diaz-Moreno
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Contributions

Introduction (C.T.C., G.B., P.D. and S.D.-M.); Experimentation (C.T.C., G.B., P.D. and S.D.-M.); Results (C.T.C., G.B., P.D. and S.D.-M.); Applications (C.T.C., G.B., P.D. and S.D.-M.); Reproducibility and data deposition (C.T.C., G.B., P.D. and S.D.-M.); Limitations and optimizations (C.T.C., G.B., P.D. and S.D.-M.); Outlook (C.T.C., G.B., P.D. and S.D.-M.); overview of the Primer (all authors).

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Correspondence to Christopher T. Chantler, Grant Bunker, Paola D’Angelo or Sofia Diaz-Moreno.

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lightsources.org: https://lightsources.org/

Mucal periodic table: http://www.csrri.iit.edu/periodic-table.html

X-ray data booklet: http://xdb.lbl.gov

Supplementary information

Glossary

χ

It is either the photoabsorption coefficient for an isolated atom with no electron interference or a semi-empirical spline or other background subtraction to approximate what this might be; or an estimated edge-jump amplitude.

Extended XAFS

(EXAFS). Refers to the region of the absorption spectrum from about 30 eV above the absorbing edge, which shows complex oscillations that explain the local order of any material, bonding and radial distances.

Fluorescence detection mode

The intensity of a particular fluorescence line emitted by the sample is measured as a function of energy. The ratio of the intensity of the fluorescence line and the intensity of the incident radiation is proportional to the absorption coefficient.

High-energy resolution fluorescence detection

The intensity of the emitted line of interest is recorded with a very narrow bandwidth as a function of the incident energy. The ratio to the incident intensity results in an X-ray absorption spectroscopy spectrum with sharper spectral features. Usually, this 1D spectrum is taken along the peak of the Kα1 or Kβ1,3 ridge to optimize flux and statistics.

k

k-space represents the spectrum in terms of the effective photoelectron wavenumber above the absorption edge E0 rather than versus energy.

Photoelectron

An electron emitted into the continuum from a bound state in the atom or material when the incident energy of the photon is above the energy of the absorption edge.

Self-absorption

Also called over-absorption. The incident photon (X-ray) field is absorbed in the material and when it emits a fluorescent photon on relaxation, the fluorescent photon is absorbed as it passes through the material to the surface.

Transmission detection mode

The absorption spectrum is obtained by taking the natural logarithm of the ratio of the intensity of the radiation before and after the sample as a function of the incident energy. The measurement obtained is equal to the absorption coefficient.

X-ray absorption fine structure

(XAFS). The modulation of the absorption coefficient at and above an absorption edge of an element owing to its chemical state and the structure of its immediate surroundings. XAFS is commonly divided into the near-edge region (X-ray absorption near-edge structure or near-edge X-ray absorption fine structure), which extends to ~30 eV above the absorption edge, and the extended region that displays oscillations in the absorption coefficient extending from 30 eV above the absorption edge.

X-ray absorption near-edge structure

(XANES); also called NEXAFS (near-edge X-ray absorption fine structure). The region of the absorption spectrum that extends from below the edge to about 30 eV above the edge. It gives insight into local coordination, molecular bonding, oxidation state, geometry and Fermi level. Sometimes referred to as the X-ray absorption main edge structure region.

X-ray absorption spectroscopy

For a solid, liquid or disordered material, the measurement of the X-ray linear absorption coefficient μpe(E) or the mass absorption coefficient as a function of incident energy E.

X-ray emission spectroscopy

The measurement of the X-ray emission from a sample irradiated by X-rays.

X-ray mass absorption coefficient

Follows the Beer–Lambert law for a beam of photons of energy E in which the transmitted photon intensity I(t) is related to the incoming photon intensity I0.

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Chantler, C.T., Bunker, G., D’Angelo, P. et al. X-ray absorption spectroscopy. Nat Rev Methods Primers 4, 89 (2024). https://doi.org/10.1038/s43586-024-00366-8

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