Comparison of the nature of π and conventional H-bonds: A theoretical investigation

P. Tarakeshwar, Kwang S. Kim

Research output: Contribution to journalArticlepeer-review

30 Scopus citations

Abstract

The interactions of the first-row hydrides (NH3, H2O, HF) with ethene have been investigated by carrying out calculations, at the second order Møller-Plesset (MP2) level of theory using both the 6-31 + G* and aug-cc-pVDZ basis sets. Unlike previous investigations of these systems, the geometries and vibrational frequencies in the present study were obtained by carrying out explicit counterpoise corrected optimizations. In an effort to understand the nature of the H···π interactions prevalent in these complexes, the interaction energies were decomposed into individual energy components using the symmetry adapted perturbation theory. Given the goals of the present investigation, the geometries, vibrational frequencies and interaction energy components of the water dimer have also been evaluated. While the interaction energy of the conventional H-bond is dominated by electrostatic interactions, electrostatic, dispersive and inductive interactions are important in the description of the π H-bond. An important distinction between conventional H-bonded complexes and the π H-bonded complexes is that the inductive interaction gets magnified at the MP2 level. Thus, the inclusion of electron correlation is an important prerequisite both for the magnification of the inductive interaction and to obtain an accurate estimate of the dispersion energies. It is observed that changes in various geometrical and vibrational parameters of these π H-bonded complexes can be correlated to the magnitude of either the individual or a combination of various interaction energy components.

Original languageEnglish (US)
Pages (from-to)227-238
Number of pages12
JournalJournal of Molecular Structure
Volume615
Issue number1-3
DOIs
StatePublished - Sep 26 2002
Externally publishedYes

Keywords

  • BSSE
  • Conventional H-bonds
  • Counterpoise corrections
  • Energy decomposition
  • Geometry optimization
  • Hydrogen bonding
  • MP2 level
  • Perturbation theory
  • SAPT
  • Van der Waals complexes
  • πH-bonds

ASJC Scopus subject areas

  • Analytical Chemistry
  • Spectroscopy
  • Organic Chemistry
  • Inorganic Chemistry

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