Energy-Degeneracy-Driven Covalency in Actinide Bonding

Jing Su, Enrique R. Batista, Kevin S. Boland, Sharon E. Bone, Joseph A. Bradley, Samantha K. Cary, David L. Clark, Steven D. Conradson, Alex S. Ditter, Nikolas Kaltsoyannis, Jason M. Keith, Andrew Kerridge, Stosh A. Kozimor, Matthias W. Löble, Richard L. Martin, Stefan G. Minasian, Veronika Mocko, Henry S. La Pierre, Gerald T. Seidler, David K. ShuhMarianne P. Wilkerson, Laura E. Wolfsberg, Ping Yang

Research output: Contribution to journalArticlepeer-review

137 Scopus citations

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 AnCl 6 2- (An IV = Th, U, Np, Pu). The results showed significant mixing between Cl 3p- and An IV 5f- and 6d-orbitals (t 1u ∗/t 2u ∗ and t 2g ∗/e g ∗), 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 An IV 6d- and Cl 3p-mixing decreased and metal 5f- and Cl 3p-orbital mixing increased across this series.

Original languageEnglish
Pages (from-to)17977-17984
Number of pages8
JournalJournal of the American Chemical Society
Volume140
Issue number51
DOIs
StatePublished - Dec 26 2018
Externally publishedYes

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