Analysis of the structures, stabilities and electronic properties of MB16− (M = V, Cr, Mn, Fe, Co, Ni) clusters and assemblies

Abstract

Doping of a cluster has often been used to stabilize and modify the structure and properties of the resulting doped cluster. In the current work, we reported the structures, stabilities and electronic properties of 3d transition metal (V, Cr, Mn, Fe, Co, Ni) atoms doped B₁₆⁻ clusters using CALYPSO searching method and density functional theory. The drum-shaped MB₁₆⁻ are favored for M = V, Cr, Mn, Fe and Co with high symmetry of C_2v, C_4v, C_4v, D_8d and D_8d symmetry respectively, while M = Ni with C_s symmetry exhibits an open bowl-shaped structure. The infrared spectra, Raman spectra and photoelectron spectra are predicted and can be used to identify the structures of these isomers from experiments. The stabilities are discussed by analyzing the binding energy, substitution reaction, HOMO–LUMO gaps and chemical hardness. In addition, electronic properties are analyzed by calculating the charge transfer, magnetic properties and chemical bonding. Finally, with the assembly of FeB₁₆⁻ and CoB₁₆⁻ drum-shaped clusters, two different Fe₂B₂₄⁻ and Co₂B₂₄⁻ clusters, which are structurally characterized as tubular forms whose triple rings are composed of three eight-membered boron rings, are identified in a high symmetry C_4v, respectively. Subsequently, the magnetic properties are investigated. The present results open a door for the discovery of more drum-shaped assemblies.