Structural and Electronic Properties of Single-Atom Transition Metal-Doped Boron Clusters MB(24) (M = Sc, V, and Mn)

[Image: see text] A theoretical study of geometrical structures, electronic properties, and spectral properties of single-atom transition metal-doped boron clusters MB(24) (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 VB(24) and MnB(24) clusters correspond to cage structures. Interestingly, the global minima obtained for the ScB(24) 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 MB(24) (M = Sc, V, and Mn) indicates that the electron delocalization of ScB(24) is stronger than that of VB(24) and MnB(24), and there is no obvious covalent bond between doped metals and B atoms. The spin density and spin population analyses reveal that MB(24) (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 MB(24) (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.