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

ABSTRACT

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.