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Updated: Jun 13, 2026

Elemental-sensitive Detection of the Chemistry in Batteries through Soft X-ray Absorption Spectroscopy and Resonant Inelastic X-ray Scattering
Published on: April 17, 2018
On the correlation between the X-ray absorption chemical shift and the formal valence state in mixed-valence
Joaquín García1, Gloria Subías, Vera Cuartero
1Instituto de Ciencia de Materiales de Aragón, CSIC-Universidad de Zaragoza, Facultad de Ciencias, Pza S. Francisco s/n, Zaragoza, Spain. jgr@unizar.es
Abstract:
Here the correlation between the chemical shift in X-ray absorption spectroscopy, the geometrical structure and the formal valence state of the Mn atom in mixed-valence manganites are discussed. It is shown that this empirical correlation can be reliably used to determine the formal valence of Mn, using either X-ray absorption spectroscopy or resonant X-ray scattering techniques. The difficulties in obtaining a reliable comparison between experimental XANES spectra and theoretical simulations on an absolute energy scale are revealed. It is concluded that the contributions from the electronic occupation and the local structure to the XANES spectra cannot be separated either experimentally or theoretically. In this way the geometrical and electronic structure of the Mn atom in mixed-valence manganites cannot be described as a bimodal distribution of the formal integer Mn(3+) and Mn(4+) valence states corresponding to the undoped references.
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