| Literature DB >> 30540455 |
Jing Su1, Enrique R Batista1, Kevin S Boland1, Sharon E Bone1, Joseph A Bradley1,2, Samantha K Cary1, David L Clark1, Steven D Conradson1, Alex S Ditter1,2, Nikolas Kaltsoyannis3, Jason M Keith1, Andrew Kerridge, Stosh A Kozimor1, Matthias W Löble1, Richard L Martin1, Stefan G Minasian1,4, Veronika Mocko1, Henry S La Pierre1, Gerald T Seidler2, David K Shuh4, Marianne P Wilkerson1, Laura E Wolfsberg1, Ping Yang1.
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.Entities:
Year: 2018 PMID： 30540455 DOI： 10.1021/jacs.8b09436
Source DB: PubMed Journal: J Am Chem Soc ISSN： 0002-7863 Impact factor: 15.419