Energy-Degeneracy-Driven Covalency in Actinide Bonding

Su, Jing and Batista, Enrqiue R. and Boland, Kevin S. and Bone, Sharon E. and Bradley, Joseph A. and Cary, Samantha K. and Clark, David L. and Conradson, Steven D. and Ditter, Alex S. and Kaltsoyannis, Nikolas and Keith, Jason M. and Kerridge, Andrew and Kozimor, Stosh A. and Loble, 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 P. and Wolfsberg, Laura E. and Yang, Ping (2018) Energy-Degeneracy-Driven Covalency in Actinide Bonding. Journal of the American Chemical Society, 140. pp. 17977-17984. ISSN 0002-7863

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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 t2g*/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.

Item Type:
Journal Article
Journal or Publication Title:
Journal of the American Chemical Society
Additional Information:
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright ©2018 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/jacs.8b09436
Uncontrolled Keywords:
/dk/atira/pure/subjectarea/asjc/1500/1503
Subjects:
ID Code:
130278
Deposited By:
Deposited On:
04 Jan 2019 09:50
Refereed?:
Yes
Published?:
Published
Last Modified:
26 Nov 2020 06:08