Oxygen K-Edge X-ray Absorption Spectra of ThO2 and CeO2: Experiment, Interpretation, and Structural Effects

Amidani, Lucia; Dumas, Thomas; Shuh, David K.; Butorin, Sergei M.; Sahle, Christoph J.; Longo, Alessandro; Kvashnina, Kristina O.

doi:10.1021/acs.jpcc.2c07771

Oxygen K-Edge X-ray Absorption Spectra of ThO₂ and CeO₂: Experiment, Interpretation, and Structural Effects

Journal Article · Wed Feb 08 00:00:00 EST 2023 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.2c07771· OSTI ID:1969344

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European Synchrotron Radiation Facility (ESRF), Grenoble (France); Helmholtz-Zentrum Dresden-Rossendorf (Germany)
Univ. Montpellier (France)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Uppsala Univ. (Sweden)
European Synchrotron Radiation Facility (ESRF), Grenoble (France)

Experimental oxygen K-edge spectra of ThO₂ and CeO₂ are presented and interpreted based on density functional theory (DFT). The contribution of d and f orbitals to the O K-edge spectrum is identified as well-distinguished peaks, the presence of which evidences the strong hybridization of Th and Ce metal centers with O orbitals. The sensitivity of the O K-edge to both f- and d-states in the absence of a core–hole on the metal ion results in an insightful overview of the electronic structure involved in the chemical bond. In particular, the large bandwidth of the Th 5f band as compared to the Ce 4f band is observed as a set of wider and more substantial set of peaks in the O K-edge, confirming the stronger hybridization of the former with O orbitals. The peak ascribed to the 5f band of ThO₂ is found at higher energy than the 6d band, as predicted from DFT calculations on actinide dioxides. Here, to highlight the sensitivity and the potential use of the O K-edge for the characterization of ThO₂-based systems, the sensitivity of the spectrum to structural changes such as lattice expansion and size reduction are calculated and discussed.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: European Research Council (ERC); Swedish Research Council; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1969344

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 6 Vol. 127; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
absorption
actinides
energy
nanoparticles
x-ray absorption near edge spectroscopy