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Covalent bonding in heavy metal oxides

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4979018· OSTI ID:1372960
 [1];  [2];  [1];  [3]
  1. Univ. of North Texas, Denton, TX (United States). Center for Advanced Scientific Computing and Modeling (CASCaM) and Dept. of Chemistry
  2. Consultant, Austin, TX (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
+ Show Author Affiliations
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.
Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1372960
Report Number(s):
PNNL-SA--123570; KC0302060
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 13 Vol. 146; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping journal July 2019
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The role of the 5f valence orbitals of early actinides in chemical bonding text January 2017

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