Covalent bonding in heavy metal oxides

Bagus, Paul S.; Nelin, Connie J.; Hrovat, Dave A.; Ilton, Eugene S.

doi:10.1063/1.4979018

Title: Covalent bonding in heavy metal oxides

Journal Article · Tue Apr 04 00:00:00 EDT 2017 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4979018· OSTI ID:1372960

^[1]; Nelin, Connie J. ^[2];

^[1]; Ilton, Eugene S. ^[3]

Univ. of North Texas, Denton, TX (United States). Center for Advanced Scientific Computing and Modeling (CASCaM) and Dept. of Chemistry
Consultant, Austin, TX (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Novel theoretical methods were used in this work to quantify the magnitude and the energetic contributions of 4f/5f-O2p and 5d/6d-O2p interactions to covalent bonding in lanthanide and actinide oxides. Although many analyses have neglected the involvement of the frontier d orbitals, the present study shows that f and d covalency are of comparable importance. Two trends are identified. As is expected, the covalent mixing is larger when the nominal oxidation state is higher. More subtly, the importance of the nf covalent mixing decreases sharply relative to (n+1)d as the nf occupation increases. Atomic properties of the metal cations that drive these trends are identified.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1372960

Report Number(s):: PNNL-SA-123570; KC0302060

Journal Information:: Journal of Chemical Physics, Vol. 146, Issue 13; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 23 works

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Extracting Chemical Information from XPS Spectra: A Perspective Bagus, Paul S.; Ilton, Eugene; Nelin, Connie J. Catalysis Letters, Vol. 148, Issue 7 https://doi.org/10.1007/s10562-018-2417-1	journal	May 2018
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
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Cluster embedding of ionic systems: Point charges and extended ions Bagus, Paul S.; Sassi, Michel J.; Rosso, Kevin M. The Journal of Chemical Physics, Vol. 151, Issue 4 https://doi.org/10.1063/1.5108728	journal	July 2019
Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping Kettner, Miroslav; Duchoň, Tomáš; Wolf, Matthew J. The Journal of Chemical Physics, Vol. 151, Issue 4 https://doi.org/10.1063/1.5109955	journal	July 2019
Analysis of the Fe 2p XPS for hematite α Fe ₂ O ₃ : Consequences of covalent bonding and orbital splittings on multiplet splittings Bagus, Paul S.; Nelin, Connie J.; Brundle, C. R. The Journal of Chemical Physics, Vol. 152, Issue 1 https://doi.org/10.1063/1.5135595	journal	January 2020
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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