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Issue 7, 2013
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Resonance-assisted hydrogen bonds revisited. Resonance stabilization vs. charge delocalization

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Abstract

The origins of stabilization in the short strong hydrogen bonds commonly referred to as “resonance-assisted” (RAHB) have been revisited using the modern valence-bond theory, the hybrid variational–perturbational interaction energy decomposition scheme and atoms in molecules (AIM) analysis. Dimers of carboxylic acids and amides have been chosen as the model structures for intermolecular RAHBs, while for the intramolecular case malondialdehyde and its substituted derivatives have been selected. The estimated (negligible) resonance stabilization energies and relative magnitudes of interaction energy components indicate that the origin of stabilization in the studied complexes is charge-delocalization. Although in the case of intramolecular RAHBs the resonance effects are much more pronounced, still they are a relatively minor contribution to the total stabilization energy. In fact, the estimated resonance stabilization energies diminish with an increasing strength of the hydrogen bond (as indicated by AIM and structural descriptors).

Graphical abstract: Resonance-assisted hydrogen bonds revisited. Resonance stabilization vs. charge delocalization

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Publication details

The article was received on 09 Oct 2012, accepted on 03 Dec 2012 and first published on 12 Dec 2012


Article type: Paper
DOI: 10.1039/C2CP43562D
Citation: Phys. Chem. Chem. Phys., 2013,15, 2514-2522
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    Resonance-assisted hydrogen bonds revisited. Resonance stabilization vs. charge delocalization

    R. W. Góra, M. Maj and S. J. Grabowski, Phys. Chem. Chem. Phys., 2013, 15, 2514
    DOI: 10.1039/C2CP43562D

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