Systematic investigation of structure and electronic properties of Cs doped anionic Bn clusters

Projects about boron-based doped of metals have constantly an important means of advancing its performance index, while bimetallic Cs atom doped of anion Bn− (n = 1–12) clusters have not been reported. In this work, the structure and electronic properties of the anionic Cs2Bn− (n = 1–12) clusters were investigated using the crystal structure analysis by particle swarm optimization (CALYPSO) structure search method and density functional theory (DFT). Theoretical calculations reveal that the most stable isomer comes from the Cs2B8− cluster with high symmetry, while the formation of two Cs atoms in different directions of pure Bn-2− is the primary structural evolution law. It is worth mentioning that the metallic character and magnetic properties of the Cs2Bn− (n = 1–12) clusters were all correspondingly enhanced after doping with Cs atoms. In addition, the dual-calibration scheme of the united photoelectron spectroscopy (PES) and infrared (IR) spectroscopy is helpful to easily verify the structural characteristics of Cs2Bn− (n = 1–12) clusters in different physical state situations. We further study the bonding characteristics of Cs2B8− clusters with high stability by using the adaptive natural density partitioning (AdNDP) and the electron localization function (ELF) methods. The results demonstrate that the 2px, 2py and part of 2s orbitals of the B-plane 2-center double-electron bond are the major contributors to the Cs2B8− cluster.