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The Boron conundrum: the case of cationic clusters B + n with n = 2–20

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Abstract

We investigate the molecular and electronic structure and thermochemical properties of the cationic boron clusters B + n with n = 2–20, using both MO and DFT methods. Several functionals are used along with the MP2, G3, G3B3, G4, and CCSD(T)/CBS methods. The latter is the high accuracy reference. While the TPSS, TPSSh, PW91, PB86, and PBE functionals show results comparable to high-accuracy MO methods, both BLYP and B3LYP functionals are not accurate enough for three-dimensional (3D) structures. A negligible difference is observed between the B3LYP, MP2, and CCSD(T) geometries. A transition between 2D and 3D structures occurs for this series at the B16 +–B19 + sizes. While smaller clusters B + n with n ≤ 15 are planar or quasi-planar, a structural competition takes place in the intermediate sizes of B +16–19 . The B20 + cation has a 3D tubular shape. The standard heats of formation are determined and used to evaluate the cluster stability. The average binding energy tends to increase with increasing size toward a limit. All closed-shell species B + n has an aromatic character, but an enhanced stability is found for B5 + and B13 + whose aromaticity and electron delocalization are analyzed using the LOL technique.

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Acknowledgments

The authors are indebted to the KULeuven Research Council for continuing support (GOA, IUAP, and IDO programs). TBT thanks the Arenberg Doctoral School of the KULeuven for a scholarship. We thank professor Arnout Ceulemans for illuminating discussion on the boron conundrum.

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Authors and Affiliations

  1. Department of Chemistry, University of Leuven, 3001, Leuven, Belgium

    Truong Ba Tai, Nguyen Minh Tam & Minh Tho Nguyen

  2. Institute for Computational Science and Technology (ICST), HoChiMinh City, Vietnam

    Nguyen Minh Tam

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  1. Truong Ba Tai
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  2. Nguyen Minh Tam
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  3. Minh Tho Nguyen
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Correspondence to Minh Tho Nguyen.

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Published as part of the special collection of articles celebrating theoretical and computational chemistry in Belgium.

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Tai, T.B., Tam, N.M. & Nguyen, M.T. The Boron conundrum: the case of cationic clusters B + n with n = 2–20. Theor Chem Acc 131, 1241 (2012). https://doi.org/10.1007/s00214-012-1241-8

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