X-Ray photoelectron spectroscopy, XPS, contains information about materials properties, especially for ionic materials of geochemical importance. However, it is difficult to relate complex XPS spectra directly to chemical properties because the spectra are composed of numerous peaks arising from the interplay of several mechanisms: (1) angular momentum coupling of the ionized core-shell with the open valence shells; (2) ligand field and spin-orbit splittings of the open valence shells; (3) many-body effects arising from nearly degenerate configurations; and, (4) covalent mixing of metal and ligand orbitals which influence XPS intensities and energies. Rigorous theory is able to relate XPS features to materials chemistry by quantifying the contributions of these mechanisms. The wavefunction based theoretical models and methods used will be described and illustrated with examples of recent studies of heavy metal oxides. This work was supported by the Geosciences Research Program, Office of Basic Energy Sciences, U. S. DOE.

Theoretical analysis of core-level spectra

245th National Meeting (2013)

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