The Hydrophobic Interaction Induced Strengthening of Hydrogen Bond in Water-DMSO Binary Mixture

TL;DR

This study reveals that hydrophobic interactions significantly strengthen water-DMSO hydrogen bonds, with lifetime and dynamics strongly dependent on composition, due to molecular self-aggregation effects analyzed through simulations.

Contribution

It introduces a new understanding of how hydrophobic interactions influence hydrogen bond strength and dynamics in water-DMSO mixtures, supported by microscopic analysis and transition state theory.

Findings

Water-DMSO hydrogen bonds have longer lifetimes than water-water bonds.

Hydrogen bond lifetime peaks at 30% DMSO concentration.

Hydrophobic methyl groups induce self-aggregation affecting bond dynamics.

Abstract

The lifetime of a hydrogen bond between water and dimethyl sulfoxide (DMSO) is found to be considerably longer than that between two water molecules in the neat water. This is counter-intuitive because the charge on the oxygen in DMSO is considerably less than that in water. Additionally, the strength of the water-dimethyl sulfoxide (w-D) hydrogen bond is found to be strongly composition dependent; the lifetime of the hydrogen bond is ten times larger at 30% over that at very low concentration. Using computer simulations, we perform microscopic structural and dynamic analysis to find that these anomalies arise at least partly from an action-at-a-distance effect where the attraction between the hydrophobic methyl groups results in self-aggregation of DMSO molecules that cages both rotational and linear motions of molecules involved. This is reflected in the observed strong correlation of the lifetime with the local coordination number of the associated methyl groups. The elongated w-D h-bond lifetime causes a slowdown of collective dynamics and affects the lifetime of the w-w h-bond. This nonlinear feedback mechanism explains the strong composition dependence of viscosity and anticipated to play a dominant role in many self-assemblies. Furthermore, the w-D hydrogen bond breaking mechanism changes from low to high DMSO concentration, a phenomenon not anticipated a priori. We introduce a new order parameter-based free energy surface of the bond breaking pathway. A two-dimensional transition state rate theory (TSRT) calculation is performed for the lifetime of the w-D h-bond that is found to be semi-quantitatively accurate