Bai, H. & Li, S. J Clust Sci (2011) 22: 525. doi:10.1007/s10876-011-0408-0
A systematic density functional theory and wave function theory investigation performed in this work reveals a planar-to-icosahedral structural transition between n = 4–5 in the partially hydrogenated B12Hn0/− clusters (n = 1–6) upon hydrogenation of all-boron B120/−. Coupled cluster calculations with triple excitations (CCSD(T)) indicate that a distorted icosahedral B12H6 cluster with C2 symmetry is overwhelmingly favored (by 35 kcal/mol) over the recently proposed perfectly planar borozene (D3h B12H6) (Szwacki et al., Nanoscale Res Lett 4:1085, 2009) which proves to be a high-lying local minimum. A similar 2D–3D structural transition occurs to the corresponding boron boronyl analogues of B12(BO)n with n –BO terminals. Detailed adaptive natural density partitioning (AdNDP) analyses reveal the bonding patterns of these quasi-planar or cage-like clusters which are characterized with delocalized σ and π molecular orbitals. The electron detachment energies of the concerned anions and excitation energies of the neutrals are also predicted to facilitate their future experimental characterizations.
BoronBoron hydridesDensity functional theoryStructuresAdaptive natural density partitioning