Geometry and electronic properties of alkali metal (rubidium) doped boron clusters

Abstract Alkali metal‐doped boron clusters have captured much attention because of their novel electronic properties and structural evolution. In the study of RbB n 0/− ( n = 2–12) clusters, the minimum global search of the potential energy surface and structure optimization at the level of PBE1PBE by using the CALYPSO method and Gaussian package coupled with DFT calculation; the geometrical structures and electronic properties are systematically investigated. At n = 8, the ground‐state structures are composed of an Rb atom above B atoms, forming a structurally stable pagoda cone. By stability analysis and charge transfer calculation, the RbB 8 − cluster shows more stability. It found that s ‐ p hybridization between Rb atom and B atoms as well as s ‐ p hybridization between B atoms is one of the reasons for the outstanding stability exhibited in the RbB 8 0/− clusters by using DOS and HOMO–LUMO orbital contour maps. The chemical bonding of the RbB 8 0/− groups was analyzed by using the AdNDP method, and B atoms with larger numbers readily form multi‐center chemical bonds with the Rb atom. From the results of the bonding analysis, the interaction between the Rb atom and B atoms strengthens the stability of the RbB 8 0/− clusters. It is hoped that this work provides a direction for experimental manipulation.