PNNL

Abstract

A single Au atom has been shown to behave like H in its bonding to Si in several mono- and disilicon gold clusters. In the current work, we investigate the Au/H analogy in trisilicon gold clusters, Si3Au3 +/0/-. Photoelectron spectroscopy and density functional calculations are combined to examine the geometric and electronic structure of Si3Au3-. We find that there are three isomers competing for the ground state of Si3Au3- as is the case for Si3H3 -. Extensive structural searches show that the potential energy surfaces of the trisilicon gold clusters _Si3Au3 -, Si3Au3, and Si3Au3+_ are similar to those of the corresponding silicon hydrides. The lowest energy isomers for Si3Au3 - and Si3Au3 are structurally similar to a Si3Au four-membered ring serving as a common structural motif. For Si3Au3 +, the 2 _ aromatic cyclotrisilenylium auride ion, analogous to the aromatic cyclotrisilenylium ion _Si3H3 +_, is the most stable species. Comparison of the structures and chemical bonding between Si3Au3 +/0/- and the corresponding silicon hydrides further extends the isolobal analogy between Au and H.