How resonance assists hydrogen bonding interactions: An energy decomposition analysis

Block‐localized wave function (BLW) method, which is a variant of the ab initio valence bond (VB) theory, was employed to explore the nature of resonance‐assisted hydrogen bonds (RAHBs) and to investigate the mechanism of synergistic interplay between π delocalization and hydrogen‐bonding interactions. We examined the dimers of formic acid, formamide, 4‐pyrimidinone, 2‐pyridinone, 2‐hydroxpyridine, and 2‐hydroxycyclopenta‐2,4‐dien‐1‐one. In addition, we studied the interactions in β‐diketone enols with a simplified model, namely the hydrogen bonds of 3‐hydroxypropenal with both ethenol and formaldehyde. The intermolecular interaction energies, either with or without the involvement of π resonance, were decomposed into the Hitler‐London energy (ΔEHL), polarization energy (ΔEpol), charge transfer energy (ΔECT), and electron correlation energy (ΔEcor) terms. This allows for the examination of the character of hydrogen bonds and the impact of π conjugation on hydrogen bonding interactions. Although it has been proposed that resonance‐assisted hydrogen bonds are accompanied with an increasing of covalency character, our analyses showed that the enhanced interactions mostly originate from the classical dipole–dipole (i.e., electrostatic) attraction, as resonance redistributes the electron density and increases the dipole moments in monomers. The covalency of hydrogen bonds, however, changes very little. This disputes the belief that RAHB is primarily covalent in nature. Accordingly, we recommend the term “resonance‐assisted binding (RAB)” instead of “resonance‐assisted hydrogen bonding (RHAB)” to highlight the electrostatic, which is a long‐range effect, rather than the electron transfer nature of the enhanced stabilization in RAHBs. © 2006 Wiley Periodicals, Inc. J Comput Chem 28: 455–466, 2007

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