The aromatic fullerene-like silicon cage with 12 Si5 pentagons stabilized by a V3 unit

Abstract

Silicon clusters doped with transition-metal (TM) atoms not only can hold stable fullerene-like structures, but also can exhibit unique electronic properties. Multiple TM doped silicon clusters are ideal models for investigating semiconductor nanomaterials and localized effects of condensed states. In this work, the geometrical and electronic properties of three V atoms doped anionic, neutral, and cationic Si20 clusters were investigated using quantum chemical calculations and a DFT-based unbiased search based on the particle swarm optimization (CALYPSO) software. The global minima of anionic, neutral, and cationic V3Si20 clusters were found to all hold a fullerene-like silicon cage with 12 Si5 pentagons stabilized by a V3 unit. The three V atoms exhibit strong interactions based on the bonding length, Wiberg bond orders, electronic charge density surfaces, and MOs. Moreover, the V atoms act as the electron acceptors on the basis of the natural population analysis (NPA), atomic dipole moment corrected Hirshfeld (ADCH) population, and atoms in molecules (AIM) population. Furthermore, V3Si20ˉ, V3Si20, and V3Si20+ show significant aromaticity according to the nucleus-independent chemical shift (NICS), aromatic stabilization energy (ASE), and multicenter bond index calculations.