Structures, stabilities and electronic properties of boron-doped silicon clusters B3Sin (n=1–17) and their anions

The structures, stabilities and electronic properties of neutral and anionic B3Sin (n = 1–17) clusters have been systemically investigated on the basis of density functional theory at the B3LYP/6-311 + G(d) level and CALYPSO structure prediction method. The structural searches show that three boron atoms tend to form B3 triangle encapsulated into Sin cages with the increasing number of silicon atoms. Most of the lowest energy structures can be derived by using the squashed pentagonal bipyramid structure of B3Si4 and B3Si4− as the major building unit. The relative stabilities are studied based on the calculated binding energies, second-order difference of energies and HOMO–LUMO gaps of the lowest energy structures. In addition, Hirshfeld, natural population analysis, Bader approaches and natural electronic configuration are performed to explore the charge transfer. At last, molecular orbital, magnetic properties, IR, Raman and UV–vis spectra are also, respectively, analysed for providing strong support for...