Computational Studies of Stable Hexanuclear CulAgmAun (l plus m plus n=6; l, m, n 0) Clusters

摘要

A DFT study was carried out on the ground state structures of ternary CulAgmAun (l+m+n-6) clusters, with the aim of investigating changes of thermal and kinetic stabilities as an effect of composition, as well as the composition dependence of the electrostatic potential, of stable planar structures. DFT optimizations were performed using the PBE functional and the SDD basis set. All the optimized structures adopt planar geometries with bent triangular structures. Calculated binding energy values are in the range 1.5-1.9 eV/atom, which shows their thermal stability. The predicted HOMO-LUMO energy gap values are in the semiconductor region, providing a qualitative indication of a moderate kinetic stability. NBO analyses indicate the existence of two mechanisms promoting planar structural stability, one due to bonding-antibonding orbital interaction, and the other one due to the well-known spd hybridization. Wiberg indices were obtained showing interatomic bonding. Electrostatic potential calculations show the existence of nucleophilic attack regions preferentially around silver and copper atoms located at the vertices while electrophilic attack regions are found in the vicinity of gold atoms over the cluster plane. Apparently, charge transfer occurs toward gold from silver and copper atoms when the concentration is favorable in the proximity of gold atoms. In particular, if the small ternary clusters discussed here contain only one gold atom, then a high electron density is observed at the site of this gold atom. (C) 2016 Wiley Periodicals, Inc.