Quantum chemical calculation studies of PdnSi12 (n = 1–3) clusters: effects of doping Pd atoms on the structural and electronic properties

Structural and electronic properties of silicon clusters doped with different number of palladium atoms, PdnSi12 (n = 1-3), are investigated using quantum chemical calculations. The most stable structures of , PdSi12, and are found to be a distorted Si-12 hexagonal prism with a Pd atom encapsulated into Si-12 cage. Further addition of the second and third Pd atoms leads to different structural evolutions for anionic, neutral, and cationic Pd2Si12 (n = 2-3) clusters. The most stable structures of both and Pd2Si12 adopt a Si-12 bicapped pentagonal prism with an edge-capping Pd atom and another Pd atom at the centre, while that of has a distorted Si-12 hexagonal prism with a Pd atom at the centre and another Pd atom edge-capping one vertical Si-Si bonds of Si-12 cage. Interestingly, the most stable structure of adopts a D-3h symmetric tritruncated trigonal bipyramid. Pd atoms in anionic, neutral, and cationic PdnSi12 (n = 2-3) clusters are found to have very weak interactions. Natural population analysis suggests that negative charges transfer from Si-12 frameworks to Pd atoms. Furthermore, the D-3h symmetric tritruncated trigonal bipyramid of exhibits significant aromaticity and sigma plus pi double bonding characters. [GRAPHICS] .