Endohedral boron-doped scandium clusters BmScn−m+/0 (m = 2–3, n = 3–13): triangular – linear rearrangement of the B3 dopant.

A theoretical investigation, employing density functional theory with the PBE functional and the Def2-TZVP basis set, comprehensively explores the geometric and electronic structures and properties of the boron doped scandium clusters BmScn−m+/0 with m = 2–3 and n = 3–13. Introduction of B atoms significantly enhances the stability of the resulting clusters with respect to the initial counterparts. As the number of B atoms increases, the stability of the doped clusters improves, following the order: B3Scn−3+/0 > B2Scn−2+/0 > BScn−1+/0 > Scn+/0. Notably, the B2@Sc8 cluster represents the smallest fully endohedral doubly doped cage, and the B3@Sc10 is the smallest fully endohedral triply doped cage reported to date. The size with 8 Sc atoms plays a crucial role in the structural evolution of both doubly doped B2Scn−2+/0 and triply doped B3Scn−3+/0 series. For the doubly doped species, this size marks an exohedral-to-endohedral transition, while in the triply doped species, it marks an interconversion of the B3 dopant from a triangular to a linear arrangement. In the triangular B3 trimer, the electron and charge distribution are evenly shared among the three B atoms, whereas in the linear B3 trimer, these distributions are unequal. Additionally, the geometric and electronic structures of the linear-B3 doped B3@Sc8 can serve as basic building blocks for the construction of larger clusters. [ABSTRACT FROM AUTHOR]