High-resolution X-ray absorption spectroscopy as a probe of crystal-field and covalency effects in actinide compounds

Butorin, Sergei M.; Kvashnina, Kristina O.; Vegelius, Johan R.; Meyer, Daniel; Shuh, David K.

doi:10.1073/pnas.1601741113

Title: High-resolution X-ray absorption spectroscopy as a probe of crystal-field and covalency effects in actinide compounds

Journal Article · Fri Jul 01 00:00:00 EDT 2016 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1601741113· OSTI ID:1379524

Butorin, Sergei M. ^[1]; Kvashnina, Kristina O. ^[2]; Vegelius, Johan R. ^[1]; Meyer, Daniel ^[3]; Shuh, David K. ^[4]

Uppsala Univ. (Sweden). Molecular and Condensed Matter Physics, Dept. of Physics and Astronomy
European Synchrotron Radiation Facility (ESRF), Grenoble (France); Helmholtz-Zentrum Dresden-Rossendorf, Dresden (Germany). Inst. of Resource Ecology
Inst. de Chimie Separative de Marcoule, Centre de Marcoule (France)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division

Applying the high-energy resolution fluorescence-detection (HERFD) mode of X-ray absorption spectroscopy (XAS), we were able to probe, for the first time to our knowledge, the crystalline electric field (CEF) splittings of the 5f shell directly in the HERFD-XAS spectra of actinides. Using ThO₂ as an example, data measured at the Th 3d edge were interpreted within the framework of the Anderson impurity model. Because the charge-transfer satellites were also resolved in the HERFD-XAS spectra, the analysis of these satellites revealed that ThO₂ is not an ionic compound as previously believed. The Th 6d occupancy in the ground state was estimated to be twice that of the Th 5f states. Here, we demonstrate that HERFD-XAS allows for characterization of the CEF interaction and degree of covalency in the ground state of actinide compounds as it is extensively done for 3d transition metal systems.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1379524

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Vol. 113, Issue 29; ISSN 0027-8424

Publisher:: National Academy of Sciences, Washington, DC (United States)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 40 works

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Cited By (5)

The role of the 5f valence orbitals of early actinides in chemical bonding Vitova, T.; Pidchenko, I.; Fellhauer, D. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms16053	journal	July 2017
A mesoporous cationic thorium-organic framework that rapidly traps anionic persistent organic pollutants Li, Yuxiang; Yang, Zaixing; Wang, Yanlong Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01208-w	journal	November 2017
Heteroleptic samarium( iii ) halide complexes probed by fluorescence-detected L ₃ -edge X-ray absorption spectroscopy Goodwin, Conrad A. P.; Réant, Benjamin L. L.; Kragskow, Jon G. C. Dalton Transactions, Vol. 47, Issue 31 https://doi.org/10.1039/c8dt01452c	journal	January 2018
Measurements of the band gap of $ThF_{4}$ by electron spectroscopy techniques Gouder, T.; Eloirdi, R.; Martin, R. L. Physical Review Research, Vol. 1, Issue 3 https://doi.org/10.1103/physrevresearch.1.033005	journal	October 2019
The role of the 5f valence orbitals of early actinides in chemical bonding Vitova, T.; Pidchenko, I.; Fellhauer, D. Karlsruhe https://doi.org/10.5445/ir/1000072139	text	January 2017

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
covalency
crystal field
actinide compounds

Title: High-resolution X-ray absorption spectroscopy as a probe of crystal-field and covalency effects in actinide compounds

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