Wang Qi, Halet Jean-François, Kahlal Samia, Muñoz-Castro Alvaro, Saillard Jean-Yves
Univ Rennes, CNRS, ISCR-UMR 6226, F-35000 Rennes, France.
Grupo de Química Inorgánica y Materiales Moleculares, Facultad de Ingenieria, Universidad Autonoma de Chile, El Llano Subercaseaux 2801, Santiago, Chile.
Phys Chem Chem Phys. 2020 Sep 23;22(36):20751-20757. doi: 10.1039/d0cp03735d.
DFT calculations were carried out on bare Au32 and Au33 nanoclusters with various charges, in order to analyze their stability with respect to different cluster electron numbers. Results indicate that in addition to the neutral Au32 hollow species, significant HOMO-LUMO gaps are computed for [Au32]8+ (hollow) and [Au32]4+ (two-shell structure). Species with smaller HOMO-LUMO gaps can reach stability upon "passivation" by a ligand shell, as experimentally exemplified. Icosahedral frameworks of Ih or lower symmetry are favored for the cationic nanoclusters whereas different structures are computed for the anionic ones.
为了分析裸Au32和Au33纳米团簇在不同簇电子数下的稳定性，对带有不同电荷的裸Au32和Au33纳米团簇进行了密度泛函理论（DFT）计算。结果表明，除了中性的Au32空心物种外，还计算出了[Au32]8+（空心）和[Au32]4+（双壳结构）具有显著的最高占据分子轨道（HOMO）-最低未占分子轨道（LUMO）能隙。如实验所示，具有较小HOMO-LUMO能隙的物种通过配体壳层“钝化”后可达到稳定状态。二十面体框架的Ih或更低对称性有利于阳离子纳米团簇，而阴离子纳米团簇则计算出不同的结构。
