A density functional theory study on the H2S molecule adsorption onto small gold clusters

An all-electron scalar relativistic calculation on AunH2S (n = 1–13) clusters has been performed by using density functional theory with the generalized gradient approximation at PW91 level. The small gold cluster would like to bond with sulfur in the same plane and the H2S molecule prefers to occupy the on-top and single fold coordination site in the cluster. The Aun structures and H2S molecule in all AunH2S clusters are only slightly perturbed and still maintain their structural integrity. After adsorption, the S–H, H–H bond-lengths and most Au–Au bond-lengths are elongated, only a few Au–Au bond-lengths far from H2S molecule are shortened. The reactivity enhancement of H2S molecule is obvious and the strong gold–sulfur bond is observed expectedly. The most favorable adsorption takes place in the case that the H2S molecule is adsorbed by an even-numbered Aun cluster and becomes AunH2S cluster with even number of valence electrons. It is believed that the strong scalar relativistic effect is favorable to H2S molecule adsorption onto small gold clusters and is also one of the important reasons for the strong gold–sulfur bond.