2024-09-03 オークリッジ国立研究所(ORNL)
＜関連情報＞
- https://www.ornl.gov/news/assorted-distinctive-behavior-molten-uranium-salt-revealed-neutrons
- https://pubs.acs.org/doi/full/10.1021/jacs.4c05765
溶融ウラン(III)塩化物における過渡的共有結合性 Transient Covalency in Molten Uranium(III) Chloride
Dmitry S. Maltsev,Darren M. Driscoll,Yuanpeng Zhang,Joerg C. Neuefeind,Benjamin Reinhart,Can Agca,Debmalya Ray,Phillip W. Halstenberg,Mina Aziziha,Juliano Schorne-Pinto,Theodore M. Besmann,Vyacheslav S. Bryantsev,Sheng Dai,Santanu Roy,and Alexander S. Ivanov,,
Journal of the American Chemical Society Published July 23, 2024
DOI:https://doi.org/10.1021/jacs.4c05765
Abstract
Uranium is arguably the most essential element in the actinide series, serving as a crucial component of nuclear fuels. While U is recognized for engaging the 5f orbitals in chemical bonds under normal conditions, little is known about its coordination chemistry and the nature of bonding interactions at extreme conditions of high temperature. Here we report experimental and computational evidence for the shrinkage of the average U–ligand distance in UCl3 upon the solid-to-molten phase transition, leading to the formation of a significant fraction of short, transient U–Cl bonds with the enhanced involvement of U 5f valence orbitals. These findings reveal that extreme temperatures create an unusual heterogeneous bonding environment around U(III) with distinct inner- and outer-coordination subshells.
