Size‐Dependent Structural Evolution and Chemical Reactivity of Gold Clusters

Abstract

Ground‐state structures and other experimentally relevant isomers of Au₁₅⁻ to Au₂₄⁻ clusters are determined through joint first‐principles density functional theory and photoelectron spectroscopy measurements. Subsequent calculations of molecular O₂ adsorption to the optimal cluster structures reveal a size‐dependent reactivity pattern that agrees well with earlier experiments. A detailed analysis of the underlying electronic structure shows that the chemical reactivity of the gold cluster anions can be elucidated in terms of a partial‐jellium picture, where delocalized electrons occupying electronic shells move over the ionic skeleton, whose geometric structure is strongly influenced by the directional bonding associated with the highly localized “d‐band” electrons.