Structures and stability of closo-hydroborate dianions BnHn2– (n = 5-12) from the PSM model

Abstract

In this theoretical study, the structures and energetic properties of several closo-hydroborate dianions BnHn2– (n = 5-12) were systematically investigated employing the B3LYP functional in conjunction with the aug-cc-pVTZ basis set. Global equilibrium geometries were determined, and the growth mechanism is established. Several thermodynamic parameters including the one-step fragmentation energy, the second-order difference in energy, and the HOMO–LUMO energy gap were also computed to evaluate their stability pattern. Computed results show that among investigated species B6H62– and B12H122– are exceptionally stable with closed-shell electronic structures. Their valence electrons generate magic numbers which could be understood by using the phenomenological shell model. The B6H62– with 26 itinerant electrons has an octahedral form ground state (Oh symmetry) and a closed electronic configuration, i.e. 1S2/1P6/2S2/1D10/2P6. Similarly, the anion B12H122– with 50 mobile electrons, which favors an icosahedron (Ih symmetry), also has a closed 1S2/1P6/2S2/1D10/2P6/1F14/2D10 electron shell. Therefore, these systems bear the highly symmetric conformations and constitute the exceedingly stable members of the series examined.