Nature of the chemical bonding in D3h [MH3M]+ cations (M = Be,Mg) |
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| Authors: | Fabio E Penotti David L Cooper Peter B Karadakov Robert Ponec |
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| Institution: | 1. Consiglio Nazionale delle Ricerche, Istituto di Scienze e Tecnologie Chimiche "Giulio Natta", Milano MI, Italy;2. Department of Chemistry, University of Liverpool, Liverpool, UK;3. Department of Chemistry, University of York, York, UK;4. Institute of Chemical Process Fundamentals, Czech Academy of Sciences Prague 6, Suchdol, Czech Republic |
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| Abstract: | Motivated by the particularly short metal-metal distance that has been predicted for the D3h BeH3Be]+ cation, comparable to those anticipated for triple bonds, we investigate the nature of the bonding interactions in the D3h MH3M]+ cations (M = Be, Mg). CCSD(T)/cc-pVQZ calculations are used to determine optimized geometries for all of the various species, including those “capped” by He or Ne atoms (as proxies for an inert gas matrix). The primary tools that are then used to investigate the nature of the chemical bonding are spin-coupled generalized valence bond calculations and the analysis of localized natural orbitals and of domain-averaged Fermi holes. The various results for all of the systems considered indicate the presence of highly polar three-center two-electron M─H─M bonding character instead of any significant direct metal-metal bonding. |
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| Keywords: | domain-averaged Fermi hole analysis localized natural orbitals spin-coupled generalized valence bond (SCGVB) calculations three-center two-electron bonding ultrashort metal-metal distances |
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