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Issue 32, 2018
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Hydrogen bonding from a valence bond theory perspective: the role of covalency

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Abstract

A valence bond theory based method has been developed to decompose hydrogen bond energies into contributions from geometry, electrostatics, polarization and charge transfer. This decomposition method has been carried out for F–H⋯FH, F–H⋯OH2, F–H⋯NH3, HO–H⋯OH2, HO–H⋯NH3, and H2N–H⋯NH3. Localized valence bond self-consistent field (L-VBSCF) and localized breathing orbital valence bond (L-BOVB) calculations were performed at the PBEPBE/aug-cc-pVDZ optimized geometries. It is shown that inclusion of valence bond structures that explicitly include charge transfer account for at least 32% (likely over half) of the hydrogen bond energy of all systems studied, indicating the dominant role of covalency. This is in agreement with calculated bond lengths, geometry deformation energies, and polarization energies. Electrostatic effects were found to play only a minor role in contrast to some widely held ideas regarding the nature of hydrogen bonding.

Graphical abstract: Hydrogen bonding from a valence bond theory perspective: the role of covalency

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Publication details

The article was received on 20 Jun 2018, accepted on 25 Jul 2018 and first published on 27 Jul 2018


Article type: Paper
DOI: 10.1039/C8CP03920H
Phys. Chem. Chem. Phys., 2018,20, 20963-20969

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    Hydrogen bonding from a valence bond theory perspective: the role of covalency

    C. T. Nemes, C. J. Laconsay and J. M. Galbraith, Phys. Chem. Chem. Phys., 2018, 20, 20963
    DOI: 10.1039/C8CP03920H

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