State‐of‐the‐art techniques for analysing X‐ray absorption spectra are reviewed, with an eye to biological applications. Recent attempts to perform full spectral fitting of the XANES energy region and beyond for the purpose of structural analysis have met with encouraging success. The present paper analyses the theoretical motivations behind this success and indicates routes for future improvements. The theoretical background is not entirely new, although the point of view is, and some sections and appendices present material that the authors believe has never been published before. The aim of this paper is to provide a theoretical analysis that is as self‐contained as possible.

A recently developed method to the full quantitative analysis of the XAS spectra extending from the absorption edge to the high-energy region is presented. This method is based on the use of two independent approaches to the analysis of the EXAFS and XANES data, the well-known GNXAS and the newly developed MXAN procedures. Herein, we report the application of this technique to two iron complexes of known structure where multiple-scattering effects are prominent, the potassium hexacyanoferrat(II) and -(III) crystals and aqueous solutions. The structural parameters obtained from refinements using the two methods are equal and compare quite well with crystallographic values. Small discrepancies between the experimental and calculated XANES spectra have been observed, and their origin has been investigated in the framework of non-muffin-tin correction. The ligand dependence of the theoretical spectra has been also examined. Analysis of the whole energy range of the XAS spectra has been found to be useful in elucidating both the type of ligands and the geometry of iron sites. These results are of particular use in studying the geometrical environment of metallic sites in proteins and complexes of chemical interest.

Abstract. We present a rigorous derivation of a real space Full-Potential MultipleScattering-Theory (FP-MST) that is free from the drawbacks that up to now have impaired its development (in particular the need to expand cell shape functions in spherical harmonics and rectangular matrices), valid both for continuum and bound states, under conditions for space-partitioning that are not excessively restrictive and easily implemented. In this connection we give a new scheme to generate local basis functions for the truncated potential cells that is simple, fast, efficient, valid for any shape of the cell and reduces to the minimum the number of spherical harmonics in the expansion of the scattering wave function. The method also avoids the need for saturating 'internal sums' due to the re-expansion of the spherical Hankel functions around another point in space (usually another cell center). Thus this approach, provides a straightforward extension of MST in the Muffin-Tin (MT) approximation, with only one truncation parameter given by the classical relation l max = kR b , where k is the electron wave vector (either in the excited or ground state of the system under consideration) and R b the radius of the bounding sphere of the scattering cell. Moreover, the scattering path operator of the theory can be found in terms of an absolutely convergent procedure in the l max → ∞ limit. Consequently, this feature provides a firm ground to the use of FP-MST as a viable method for electronic structure calculations and makes possible the computation of x-ray spectroscopies, notably photo-electron diffraction, absorption and anomalous scattering among others, with the ease and versatility of the corresponding MT theory. Some numerical applications of the theory are presented, both for continuum and bound states.

A full multiple theoretical model (MXAN) is applied to fit picosecond difference X-ray absorption spectra at the ruthenium L(3) edge upon photoexcitation of aqueous [RuII(bpy)3]2+. We show that fitting difference spectra allows an increase in sensitivity, such that slight structural changes can be retrieved, which are not detected in fitting full spectra. The Ru-N bond distances of the excited complex in the (3)MLCT state are in good agreement with recently published values. The implementation of the present approach to L-edge spectra and its high sensitivity opens opportunities for its extension to a large class of experiments where difference X-ray absorption spectra are recorded.