Abstract

Two aspects of the electronic structure of actinide oxides that significantly affect the X-ray photoelectron spectroscopy (XPS) spectra are described; these aspects are also important for the materials properties of the oxides. The two aspects considered are: (1) The spin–orbit coupling of the open 5f shell electrons in actinide cations and how this coupling affects the electronic structure. And, (2) the covalent character of the metal oxygen interaction in actinide compounds. Because of this covalent character, there are strong departures from the nominal oxidation states that are significantly larger in core–hole states than in the ground state. The consequences of this covalent character for the XPS are examined. A proper understanding of the way in which they influence the XPS makes it possible to use the XPS to correctly characterize the electronic structure of the oxides.

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