Structure evolution of chromium-doped boron clusters: Toward the formation of endohedral boron cages

Abstract

The electron-deficient nature of boron endows isolated boron clusters with a variety of interesting structural and bonding properties that can be further enriched through metal doping. In the current work, we report the structural and electronic properties of a series of chromium-doped boron clusters. The global minimum structures for CrB n clusters with an even number of n ranging from 8 to 22 are proposed through extensive first-principles swarm-intelligence structure searches. Half-sandwich structures are found to be preferred for CrB 8 , CrB 10 , CrB 12 and CrB 14 clusters and to transform to a drum-like structure at CrB 16 cluster. Endohedral cage structures with the Cr atom located at the center are energetically most favorable for CrB 20 and CrB 22 clusters. Notably, the endohedral CrB 20 cage has a high symmetry of D 2d and a large HOMO-LUMO gap of 4.38 eV, whose stability is attributed to geometric fit and formation of an 18-electron closed-shell configuration. The current results advance our understanding of the structure and bonding of metal-doped boron clusters.