Probing the 2 Dto-3 D structural transition in gold clusters with a single sulfur atom : Au x S 0 , 1 ( x 1⁄4 1 – 10 )

Gold sulfur clusters have received much attention because of the dramatic effect that the gold–sulfide interaction produces in thiol-passivated gold nanoparticles. We present a systematic theoretical study of the electronic properties and geometric structures of AuxS 0, 1 (x 1⁄4 1–10) clusters using the basinhopping global optimization technique coupled with density functional theory (DFT-BH) methods. Higher-level ab initio calculations are performed to aid in structural assignment. The same species with different electric charges possess different configurations. The 2D-to-3D structural transitions of the global minimum structures of cationic, neutral, and anionic AuxS clusters are found at the sizes of x 1⁄4 3, 6, and 9, respectively. It is found that the Au5S cluster can be regarded as the building-block unit for the evolution of larger Au–S clusters. The tendency toward planarity of each Au–S cluster species, which is similar to that of bare Au clusters, may be attributed to the strong relativistic effects of Au and the similar electronegativity between Au and S. The trends of the binding energies, electron affinities, and bond parameters with increasing cluster size are studied in detail for each species. The results demonstrate that the binding energies and second-order differences exhibit interesting oscillatory behaviors; it is believed that anionic clusters may be the most suitable for catalysis.