Structural Evolution and Superatoms in Molybdenum Atom Stabilized Boron Clusters: MoBn (n =10-24)

Doping transition metal atom is known as an effective approach to stabilize an atomic cluster and modify its structure and electronic properties. We herein report the effect of molybdenum doping on the structural evolution of medium-sized boron clusters. The lowest-energy structures of MoBn (n = 10, 12, 14, 16, 18, 20, 22, 24) clusters are globally searched using genetic algorithm combined with density functional theory calculations. We found that Mo doping has significantly affected the grow behaviors of B-n clusters, leading to a structural evolution from bowl-like to tubular and finally endohedral cage. The size-dependent binding energy, HOMO-LUMO gap, vertical ionization potential and vertical electron affinity show that MoB12, MoB22 and MoB24 clusters have relatively higher stability and enhanced chemical inertness. More interestingly, the endohedral MoB22 cage is identified as an elegant superatom, which satisfies 18-electron closed shell configuration well.