Energy-Degeneracy-Driven Covalency in Actinide Bonding
Abstract
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.
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- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Washington, Seattle, WA (United States)
- Univ. of Manchester (United Kingdom)
- Lancaster Univ. (United Kingdom)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Univ. of Washington, Seattle, WA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1489963
- Alternate Identifier(s):
- OSTI ID: 1505523
- Report Number(s):
- LA-UR-18-28062
Journal ID: ISSN 0002-7863
- Grant/Contract Number:
- 89233218CNA000001; AC52-06NA25396; AC02-05CH11231; AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 140; Journal Issue: 51; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Actinium, plutonium, neptunium, uranium, thorium, Cl K-edge XAS, TDDFT, XANES
Citation Formats
Su, Jing, Batista, Enrique Ricardo, Boland, Kevin Sean, Bone, Sharon E., Bradley, Joseph A., Cary, Samantha K., Clark, David Lewis, Conradson, Steven Daniel, Ditter, Alexander Scott, Kaltsoyannis, Nikolas, Keith, Jason M., Kerridge, Andrew, Kozimor, Stosh Anthony, Loeble, Matthias W., Martin, Richard L., Minasian, Stefan G., Mocko, Veronika, La Pierre, Henry S., Seidler, Gerald T., Shuh, David K., Wilkerson, Marianne Perry, Wolfsberg, Laura Evon, and Yang, Ping. Energy-Degeneracy-Driven Covalency in Actinide Bonding. United States: N. p., 2018.
Web. doi:10.1021/jacs.8b09436.
Su, Jing, Batista, Enrique Ricardo, Boland, Kevin Sean, Bone, Sharon E., Bradley, Joseph A., Cary, Samantha K., Clark, David Lewis, Conradson, Steven Daniel, Ditter, Alexander Scott, Kaltsoyannis, Nikolas, Keith, Jason M., Kerridge, Andrew, Kozimor, Stosh Anthony, Loeble, Matthias W., Martin, Richard L., Minasian, Stefan G., Mocko, Veronika, La Pierre, Henry S., Seidler, Gerald T., Shuh, David K., Wilkerson, Marianne Perry, Wolfsberg, Laura Evon, & Yang, Ping. Energy-Degeneracy-Driven Covalency in Actinide Bonding. United States. https://doi.org/10.1021/jacs.8b09436
Su, Jing, Batista, Enrique Ricardo, Boland, Kevin Sean, Bone, Sharon E., Bradley, Joseph A., Cary, Samantha K., Clark, David Lewis, Conradson, Steven Daniel, Ditter, Alexander Scott, Kaltsoyannis, Nikolas, Keith, Jason M., Kerridge, Andrew, Kozimor, Stosh Anthony, Loeble, Matthias W., Martin, Richard L., Minasian, Stefan G., Mocko, Veronika, La Pierre, Henry S., Seidler, Gerald T., Shuh, David K., Wilkerson, Marianne Perry, Wolfsberg, Laura Evon, and Yang, Ping. Wed .
"Energy-Degeneracy-Driven Covalency in Actinide Bonding". United States. https://doi.org/10.1021/jacs.8b09436. https://www.osti.gov/servlets/purl/1489963.
@article{osti_1489963,
title = {Energy-Degeneracy-Driven Covalency in Actinide Bonding},
author = {Su, Jing and Batista, Enrique Ricardo and Boland, Kevin Sean and Bone, Sharon E. and Bradley, Joseph A. and Cary, Samantha K. and Clark, David Lewis and Conradson, Steven Daniel and Ditter, Alexander Scott and Kaltsoyannis, Nikolas and Keith, Jason M. and Kerridge, Andrew and Kozimor, Stosh Anthony and Loeble, Matthias W. and Martin, Richard L. and Minasian, Stefan G. and Mocko, Veronika and La Pierre, Henry S. and Seidler, Gerald T. and Shuh, David K. and Wilkerson, Marianne Perry and Wolfsberg, Laura Evon and Yang, Ping},
abstractNote = {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.},
doi = {10.1021/jacs.8b09436},
journal = {Journal of the American Chemical Society},
number = 51,
volume = 140,
place = {United States},
year = {Wed Dec 12 00:00:00 EST 2018},
month = {Wed Dec 12 00:00:00 EST 2018}
}
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