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Interplay between hydrogen bond formation and multicenter pi-electron delocalization: Intermolecular hydrogen bonds
Journal Contribution - Journal Article
The interplay between aromatic electron delocalization and intermolecular hydrogen bonding is thoroughly
investigated using multicenter delocalization analysis. The effect on the hydrogen bond strength of aromatic
electron delocalization within the acceptor and donor molecules is determined by means of the interaction
energies between monomers, calculated at the B3LYP/6-311++G(d,p) level of theory. This magnitude is
compared to variations of multicenter electron delocalization indices and covalent hydrogen bond indices,
which are shown to correlate perfectly with the relative values of the interaction energies for the different
complexes studied. The multicenter electron delocalization indices and covalent bond indices have been
computed using the quantum theory of atoms in molecules approach. All the hydrogen bonds are formed
with oxygen as the acceptor atom; however, the atom bonded to the donor hydrogen has been either oxygen
or nitrogen. The water-water complex is taken as reference, where the donor and acceptor molecular
environments are modified by substituting the hydrogens and the hydroxyl group by phenol, furan, and pyrrole
aromatic rings. The results here shown match perfectly with the qualitative expectations derived from the
resonance model.
Journal: JOURNAL OF PHYSICAL CHEMISTRY A
ISSN: 1089-5639
Issue: 34
Volume: 112
Pages: 7898 - 7904
Publication year:2008