Geometries, stabilities and electronic properties of small-sized Pd2-doped Sin (n = 1–11) clusters

Abstract

The geometries, growth patterns, relative stabilities and electronic properties of small-sized Pd2Sin and Sin+2 (n = 1–11) clusters are systematically studied using the hybrid density functional theory method B3LYP. The optimised structures revealed that the lowest energy Pd2Sin clusters are not similar to those of pure Sin clusters. When n = 9, one Pd atom in Pd2Si9 completely falls into the centre of the Si outer frame, forming metal-encapsulated Si cages. On the basis of the optimised structures, the averaged binding energy, fragmentation energy, second-order energy difference and highest occupied–lowest unoccupied molecular orbital energy gap are calculated. It is found that the Pd2Si5 and Pd2Si7 clusters have stronger relative stabilities among the Pd2Sin clusters. Additionally, the stabilities of Sin+2 clusters have been reduced by the doping of Pd impurity. The natural population and natural electronic configuration analysis indicated that the Pd atoms possess negative charges for n = 1–11 and there exist the spd hybridisation in the Pd atom. Finally, the chemical hardness, chemical potential, electrostatic potential and polarisability are discussed.