Structural and Electronic Properties of Single-Atom Transition Metal-Doped Boron Clusters MB₂₄ (M = Sc, V, and Mn)

A theoretical study of geometrical structures, electronic properties, and spectral properties of single-atom transition metal-doped boron clusters MB₂₄ (M = Sc, V, and Mn) is performed using the CALYPSO approach for the global minimum search, followed by density functional theory calculations. The global minima obtained for the VB₂₄ and MnB₂₄ clusters correspond to cage structures. Interestingly, the global minima obtained for the ScB₂₄ cluster tend to a three-ring tubular structure. Population analyses and valence electron density analyses reveal that partial electrons on transition-metal atoms transfer to boron atoms. The localized orbital locator of MB₂₄ (M = Sc, V, and Mn) indicates that the electron delocalization of ScB₂₄ is stronger than that of VB₂₄ and MnB₂₄, and there is no obvious covalent bond between doped metals and B atoms. The spin density and spin population analyses reveal that MB₂₄ (M = Sc, V, and Mn) have different spin characteristics which are expected to lead to interesting magnetic properties and potential applications in molecular devices. The calculated spectra indicate that MB₂₄ (M = Sc, V, and Mn) has meaningful characteristic peaks that can be compared with future experimental values and provide a theoretical basis for the identification and confirmation of these single-atom transition metal-doped boron clusters. Our work enriches the database of geometrical structures of doped boron clusters and can provide an insight into new doped boron clusters.