Probing the structural, electronic, and adsorptive properties of Au₁₆O₂^- clusters

Great progress has been made in O₂ adsorption on gold clusters. However, systematic investigations of O₂ adsorption on [Formula: see text] clusters have not been reported. Here, we present a systematic study of the structural, electronic, and adsorptive properties of [Formula: see text] clusters by density functional theory (DFT) calculations coupled with stochastic kicking method. Global minimum searches for [Formula: see text] reveal that exohedral derivatives are more favored. Furthermore, the obtained ground-state structure exhibits significant stability, as judged by its larger adsorption energy (1.16 eV) and a larger HOMO-LUMO gap (0.57 eV). The simulated photoelectron spectra (PES) of [Formula: see text] isomers will be instructive to identify the structures in future experiments. There are three interesting discoveries in the present paper: (1) O₂ undergoes chemical adsorption onto the parent [Formula: see text] clusters, but the amount of the adsorption energy is related to the parent [Formula: see text] clusters; (2) the process that O₂ undergoes dissociative adsorption onto the parent [Formula: see text] clusters is exothermic; (3) [Formula: see text] isomers show smaller X-A energy gaps than those of parent [Formula: see text] clusters, reflecting that their geometric and electronic structures are distorted remarkably due to dissociative adsorption of O₂.