Ion diffusion captures composition-dependent anomalies in water–DMSO binary mixtures

Abstract

Aqueous dimethyl sulfoxide (Aq-DMSO) binary mixture exhibits many fascinating composition-dependent anomalies that are explained by using the peculiarities of the water–DMSO hydrogen bond. Ions can couple strongly to these composition-dependent anomalies to produce exotic dynamics of their own. We carry out theoretical studies using computer simulations to understand the structural and dynamical aspects of rigid monovalent cations (Li+, Na+, K+, Rb+, and Cs+) in aqueous DMSO solutions, with chloride as the counterion. We uncover a number of composition-dependent ion diffusion anomalies, which can be traced back to the interplay between the size-dependent charge density of the ion and the resulting difference in interactions of the ion with water and DMSO molecules. Size and composition dependence of the diffusion coefficients of the five ions exhibit fascinating variations that can be explained partially.