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Title: Energy-Degeneracy-Driven Covalency in Actinide Bonding

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.8b09436· OSTI ID:1489963
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1];  [2]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [1];  [4]; ORCiD logo [1];  [1];  [1]; ORCiD logo [5]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [6];  [7] more »; ORCiD logo [1];  [1]; ORCiD logo [1] « less
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Washington, Seattle, WA (United States)
  3. Univ. of Manchester (United Kingdom)
  4. Lancaster Univ. (United Kingdom)
  5. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  6. Univ. of Washington, Seattle, WA (United States)
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
+ Show Author Affiliations

Evaluating the nature of chemical bonding for actinide elements represents one of the most important and long-standing problems in actinide science. We directly address this challenge and contribute a Cl K-edge X-ray absorption spectroscopy and relativistic density functional theory study that quantitatively evaluates An-Cl covalency in AnCl62- (AnIV = Th, U, Np, Pu). The results showed significant mixing between Cl 3p- and AnIV 5f- and 6d-orbitals (t1u*/t2u* and t2 g*/eg *), with the 6d-orbitals showing more pronounced covalent bonding than the 5f-orbitals. Moving from Th to U, Np, and Pu markedly changed the amount of M-Cl orbital mixing, such that AnIV 6d - and Cl 3p-mixing decreased and metal 5f - and Cl 3p-orbital mixing increased across this series.

Research Organization:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
89233218CNA000001; AC52-06NA25396; AC02-05CH11231; AC02-76SF00515
OSTI ID:
1489963
Alternate ID(s):
OSTI ID: 1505523
Report Number(s):
LA-UR-18-28062
Journal Information:
Journal of the American Chemical Society, Vol. 140, Issue 51; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 70 works
Citation information provided by
Web of Science

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Cited By (3)

Actinide 2-metallabiphenylenes that satisfy Hückel’s rule journal February 2020
Lanthanide and actinide doped B 12 H 12 2− and Al 12 H 12 2− clusters: new magnetic superatoms with f-block elements journal January 2019
Tuning the structure, reactivity and magnetic communication of nitride-bridged uranium complexes with the ancillary ligands journal January 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Actinium
plutonium
neptunium
uranium
thorium
Cl K-edge XAS
TDDFT
XANES