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XPS determination of uranium oxidation states
Author(s) -
Ilton Eugene S.,
Bagus Paul S.
Publication year - 2011
Publication title -
surface and interface analysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.52
H-Index - 90
eISSN - 1096-9918
pISSN - 0142-2421
DOI - 10.1002/sia.3836
Subject(s) - x ray photoelectron spectroscopy , valence (chemistry) , oxidation state , binding energy , chemistry , uranium , oxide , hydroxide , spectroscopy , hydrate , analytical chemistry (journal) , inorganic chemistry , atomic physics , materials science , metal , nuclear magnetic resonance , physics , environmental chemistry , metallurgy , organic chemistry , quantum mechanics
This contribution is both a review of different aspects of X‐ray photoelectron spectroscopy that can help one determine U oxidation states and a personal perspective on how to effectively model the X‐ray photoelectron spectroscopy of complicated mixed‐valence U phases. After a discussion of the valence band, the focus lingers on the U4f region, where the use of binding energies, satellite structures, and peak shapes is discussed in some detail. Binding energies were shown to be very dependent on composition/structure and consequently unreliable guides to oxidation state, particularly where assignment of composition is difficult. Likewise, the spin orbit split 4f 7/2 and 4f 5/2 peak shapes do not carry significant information on oxidation states. In contrast, both satellite‐primary peak binding energy separations, as well as intensities to a lesser extent, are relatively insensitive to composition/structure within the oxide–hydroxide–hydrate system and can be used to both identify and help quantify U oxidation states in mixed valence phases. An example of the usefulness of the satellite structure in constraining the interpretation of a complex multivalence U compound is given. Copyright © 2011 John Wiley & Sons, Ltd.