Theoretical Chemistry Accounts

, 131:1088

Proton-bound homodimers involving second-row atoms

Regular Article

DOI: 10.1007/s00214-012-1088-z

Cite this article as:
Chan, B., Del Bene, J.E. & Radom, L. Theor Chem Acc (2012) 131: 1088. doi:10.1007/s00214-012-1088-z
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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.


Hydrogen bondingAb initioHomodimersBinding energiesStructures

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© Springer-Verlag 2012

Authors and Affiliations

  1. 1.School of Chemistry and ARC Centre of Excellence for Free Radical Chemistry and BiotechnologyUniversity of SydneySydneyAustralia
  2. 2.Department of ChemistryYoungstown State UniversityYoungstownUSA