Abstract: The geometries, stabilities, and electronic properties of Au₁₂M (M=Na, Mg, Al, Si, P, S, Cl) clusters were systematically investigated by using first-principles calculations based on density functional theory (DFT). For each cluster, the average binding energy, the embedding energy, the vertical ionization potential, the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), the natural charge population analysis, and the natural bond orbital analysis (NBO) were calculated. The lowest-energy structures of Au₁₂M (M=Na, Mg, Al) clusters are cages with M encapsulated in the center, while structures of Au₁₂M (M=Si, P, S, Cl) clusters are pyramidal with M at the apex. The Au₁₂S cluster, having the full closed-shells, is the most stable. Furthermore, from the natural population analysis, it follows that charges transfer from Au to M in all the clusters. The NBO and HOMO analyses reveal that hybridization occurs between the Au s-d orbitals and the M p orbitals.

Key words: Density functional theory, Cluster, Natural charge population analysis, Stability, Natural bond orbital analysis