Theoretical Study on Geometric Structures, Electronic, and Thermodynamics Properties of VB2n- (n=8-12) Clusters

The geometric structures, electronic, and thermodynamic properties of vanadium doped boron clusters, VB2n- (n=8-12), were investigated systemically by using CALYPSO searching method and density functional theory. It is found that vanadium atom doping significantly modifies the structures of the boron clusters and strong the chemical activity of systems. A drum-shaped structure is the global minimum for VB16- cluster with C-2v point symmetry. Tubular-shaped VB18- and VB20- with C-2v and C-s symmetry exhibit a metal-centred tubular with a B-2 unit over the B-16 and B-18 drum, respectively. For VB22- and VB24- clusters, vanadium atom tends to encapsulate into boron cages. Based on the lowest energy structures, the charge transfer and polarizability were explored, the photoelectron spectra, infrared spectra, and Raman spectra were simulated, the fluxional bonds and aromatic properties were analyzed. At last, the thermodynamic properties were investigated, the thermodynamics parameters were discussed for the lowest energy structures of VB2n- (n=8-12) clusters.