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 language | English |
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Pages (from-to) | 17977-17984 |
Number of pages | 8 |
Journal | Journal of the American Chemical Society |
Volume | 140 |
Issue number | 51 |
DOIs | |
State | Published - Dec 26 2018 |
Externally published | Yes |