Is Electrostatics Sufficient to Describe Hydrogen‐Bonding Interactions?

Abstract

The stability and geometry of a hydrogen-bonded dimer is traditionally attributed mainly to the central moiety A-H⋅⋅⋅B, and is often discussed only in terms of electrostatic interactions. The influence of substituents and of interactions other than electrostatic ones on the stability and geometry of hydrogen-bonded complexes has seldom been addressed. An analysis of the interaction energy in the water dimer and several alcohol dimers--performed in the present work by using symmetry-adapted perturbation theory--shows that the size and shape of substituents strongly influence the stabilization of hydrogen-bonded complexes. The larger and bulkier the substituents are, the more important the attractive dispersion interaction is, which eventually becomes of the same magnitude as the total stabilization energy. Electrostatics alone are a poor predictor of the hydrogen-bond stability trends in the sequence of dimers investigated, and in fact, dispersion interactions predict these trends better.