Ab initio calculation of geometries, stabilities, and electronic properties for bimetallic Cs2-doped gold clusters: comparison with pure gold clusters

Abstract

The geometrical structures, relative stabilities, and electronic properties of pure and Cs2-doped gold clusters have been determined by employing the density functional method with the relativistic effective core potential. The results show that doping with two Cs atoms dramatically affects the geometries of the ground-state pure gold clusters and the doped Cs atoms prefer to locate at the symmetry position. The relative stability of these clusters is examined via analysis of the averaged atomic binding energies, fragmentation energies, the second-order difference of energies and the highest occupied–lowest unoccupied molecular orbital energy gaps as a function of cluster size. The results exhibit a dramatic even–odd alternative behavior. In particular, it should be noted that a maximum peak is observed for Cs2Au n clusters at n = 2, implying that the Cs2Au2 cluster possesses relatively higher stability. In addition, the charge transfers, VIPs, VEAs, chemical hardnesses and polarizabilities have been analysed and compared.