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Hydrogenation of B 0/−12 : A Planar-to-Icosahedral Structural Transition in B12H 0/− n (n = 1–6) Boron Hydride Clusters

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Abstract

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 B12H 0/− n clusters (n = 1–6) upon hydrogenation of all-boron B 0/−12 . 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.

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Acknowledgments

This work was jointly supported by the National Science Foundation of China (No. 20873117) and Shanxi Natural Science Foundation (No. 2010011012-3). The authors are grateful to Professor A. I. Boldyrev and Dr. T. Galeev and A. Sergeeva at Utah State University for their generous help in using the AdNDP program.

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Authors and Affiliations

  1. Institute of Molecular Sciences, Shanxi University, Taiyuan, 030006, Shanxi, People’s Republic of China

    Hui Bai & Si-Dian Li

  2. Department of Chemistry, Institute of Materials Science, Xinzhou Teachers’ University, Xinzhou, 034000, Shanxi, People’s Republic of China

    Hui Bai & Si-Dian Li

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  1. Hui Bai
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  2. Si-Dian Li
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Correspondence to Si-Dian Li.

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Bai, H., Li, SD. Hydrogenation of B 0/−12 : A Planar-to-Icosahedral Structural Transition in B12H 0/− n (n = 1–6) Boron Hydride Clusters. J Clust Sci 22, 525–535 (2011). https://doi.org/10.1007/s10876-011-0408-0

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