X‐Ray Absorption Spectroscopy of Amorphous Solids, Liquids, and Catalytic and Biochemical Systems—Capabilities and Limitations

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Abstract
Although the effect on which X‐ray absorption spectroscopy (EXAFS spectroscopy) is based has been known for about 70 years, up until about 20 years ago it had not found any application. The reasons for this were on the one hand the shortage of efficient X‐ray sources, and on the other hand the lack of a suitable theoretical description. With the advent of synchrotron radiation the situation has changed completely. Today, EXAFS spectroscopy is applied to a variety of very different problems and used more and more frequently to answer chemical questions. The extraordinary behavior of EXAFS spectroscopy that allows the determination of local structures in almost any mixture, independent of the sample's physical state as well as element‐specifically with high sensitivity, carries with it the danger that the amount of the obtainable structural information will be overestimated. A realistic estimate of the capability of EXAFS spectroscopy has in the meantime been achieved for crystalline materials, but not for amorphous materials. In this case the viewpoints range from complete rejection to overinterpretation of the EXAFS spectrum. In this article an attempt is made to show how EXAFS spectroscopy can be applied in the investigation of noncrystalline materials. First, the measurement techniques, data analysis procedures, and the simulation of EXAFS spectra are explained. Starting with the simplest systems, the amorphous metals and nonmetals, and using representative but not necessarily current examples, an explanation is given of the structural information provided by EXAFS spectroscopy, of how the local environment about the two components can be determined in binary systems, and of how even the crystallization process and structural changes can be investigated in chemical reactions. Thereafter, EXAFS studies on solutions, molecular liquids, and melts are presented. The final section is concerned with typical applications of EXAFS spectroscopy, the investigation of homogeneous and heterogeneous catalysts as well as the elucidation of active sites in enzymes.

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