Electron count and electronic structure of bare icosahedral Au32 and Au33 ionic nanoclusters and ligated derivatives. Stable models with intermediate superatomic shell fillings

Abstract

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 I_h or lower symmetry are favored for the cationic nanoclusters whereas different structures are computed for the anionic ones.