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Computational and Spectroscopic Tools for the Detection of Bond Covalency in Pu(IV) Materials

Bagus, Paul S.; Schacherl, Bianca ORCID iD icon; Vitova, Tonya ORCID iD icon


Plutonium is used as a major component of new-generation nuclear fuels and of radioisotope batteries for Mars rovers, but it is also an environmental pollutant. Plutonium clearly has high technological and environmental importance, but it has an extremely complex, not well-understood electronic structure. The level of covalency of the Pu 5f valence orbitals and their role in chemical bonding are still an enigma and thus at the frontier of research in actinide science. We performed fully relativistic quantum chemical computations of the electronic structure of the Pu4+ ion and the PuO2 compound. Using four different theoretical tools, it is shown that the 5f orbitals have very little covalent character although the 5f(7/2) a2u orbital with the highest orbital energy has the greatest extent of covalency in PuO2. It is illustrated that the Pu M4,5 edge high-energy resolution X-ray absorption near-edge structure (Pu M4,5 HR-XANES) spectra cannot be interpreted in terms of dipole selection rules applied between individual 3d and 5f orbitals, but the selection rules must be applied between the total wavefunctions for the initial and excited states. ... mehr

Verlagsausgabe §
DOI: 10.5445/IR/1000139992
Veröffentlicht am 12.11.2021
DOI: 10.1021/acs.inorgchem.1c01331
Zitationen: 8
Web of Science
Zitationen: 7
Zitationen: 9
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nukleare Entsorgung (INE)
Publikationstyp Zeitschriftenaufsatz
Publikationsmonat/-jahr 11.2021
Sprache Englisch
Identifikator ISSN: 0020-1669, 1520-510X
KITopen-ID: 1000139992
HGF-Programm 32.11.01 (POF IV, LK 01) Nuclear Waste Disposal
Weitere HGF-Programme 54.11.11 (POF IV, LK 01) Accelerator Operation, Research and Development
Erschienen in Inorganic chemistry
Verlag American Chemical Society (ACS)
Band 60
Heft 21
Seiten 16090–16102
Vorab online veröffentlicht am 11.10.2021
Nachgewiesen in Scopus
Web of Science
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