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

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 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 CrB₈, CrB₁₀, CrB₁₂ and CrB₁₄ clusters and to transform to a drum-like structure at CrB₁₆ cluster. Endohedral cage structures with the Cr atom located at the center are energetically most favorable for CrB₂₀ and CrB₂₂ clusters. Notably, the endohedral CrB₂₀ 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.