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Proton-bound homodimers involving second-row atoms

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Abstract

High-level ab initio quantum chemical calculations (G4(MP2)//MP2/6-311+G(2df,p)) have been used to examine homodimers of second-row bases, and to compare the results with those obtained previously for the first-row analogs. The relationship between the binding energies of the dimers and the proton affinities (PAs) of the bases follows the same pattern as that for the first-row systems, with the binding energies initially increasing with increasing proton affinity but subsequently decreasing. This may be attributed to the opposing effects of increased PA on the hydrogen-bond donor and hydrogen-bond acceptor. The binding energies are generally smaller for the second-row dimers than for the corresponding first-row dimers. There is an increased tendency for asymmetrical hydrogen bonds in homodimers of the second-row compared with first-row dimers. This may be attributed to the lower electronegativities of second-row atoms relative to their first-row counterparts, and to the longer internuclear separation between the hydrogen-bonded second-row atoms.

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Acknowledgments

We gratefully acknowledge the award of an Australian Professorial Fellowship and funding from the ARC Centre of Excellence for Free Radical Chemistry and Biotechnology (to L.R.), and generous allocations of computer time from the National Computational Infrastructure (NCI) National Facility and Intersect Australia Ltd, and from the Ohio Supercomputer Center.

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Authors and Affiliations

  1. School of Chemistry and ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, University of Sydney, Sydney, NSW, 2006, Australia

    Bun Chan & Leo Radom

  2. Department of Chemistry, Youngstown State University, Youngstown, OH, 44555, USA

    Janet E. Del Bene

Authors
  1. Bun Chan
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  2. Janet E. Del Bene
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  3. Leo Radom
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Correspondence to Bun Chan, Janet E. Del Bene or Leo Radom.

Additional information

Dedicated to Professor Eluvathingal Jemmis and published as part of the special collection of articles celebrating his 60th birthday.

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Chan, B., Del Bene, J.E. & Radom, L. Proton-bound homodimers involving second-row atoms. Theor Chem Acc 131, 1088 (2012). https://doi.org/10.1007/s00214-012-1088-z

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