Theoretical studies on the oxidation states and electronic structures of actinide-borides: AnB12 (An = Th-Cm) clusters

Physical Chemistry Chemical Physics : PCCP
Shu-Xian HuBingyun Ao

Abstract

As B12 clusters exhibit significant structural stability due to double aromaticity, metal doped-B12 clusters often prefer a half sandwich structure. Herein, we report a systematic theoretical study on the geometric and electronic structures, and chemical bonding of the half sandwich AnB12 (An = Th to Cm) clusters to explore the stability and extent of covalency of the An-B bonds of these actinide borides. We have shown that in the gas-phase clusters, the significant stability of AnB12 is determined by electrostatic and orbital interactions between the An 5f6d7s orbitals and π-type molecular orbitals from B 2p orbitals of the B12 unit. A change-over of An-B bond length from An = Th to Cm is found at An = Pa as a result of actinide contraction combined with weakening An-B bonding due to an energy decrease and orbital localization of the 5f orbitals. Consistently, the oxidation states of the An atoms at first increase from Th(f0)IV to Pa(f0)V, and then due to the 5f-AO contraction, they smoothly decline to U(f2)IV, Np(f4)III and Pu(f5)III, and then eventually to Am(f7)II but Cm(f7)III, both with a half-filled 5f shell.

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Citations

Nov 15, 2018·Physical Chemistry Chemical Physics : PCCP·Bingyun AoShu-Xian Hu
Jul 19, 2019·The Journal of Physical Chemistry. a·Jian-Wei QinShu-Xian Hu
Nov 30, 2021·Physical Chemistry Chemical Physics : PCCP·Juan WangWei-Qun Shi
Jan 19, 2022·Inorganic Chemistry·Ke ZhouShu-Xian Hu

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Software Mentioned

Molpro
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