Rigid Cations Induce Enhancement of Microheterogeneity and Exhibit Anomalous Ion Diffusion in Water-Ethanol Mixtures.

Because of the amphiphilic nature of ethanol in the aqueous solution, ions cause an interesting microheterogeneity where the water molecules and the hydroxy groups of ethanol preferentially solvate the ions, while the ethyl groups tend to occupy the intervening space. Using computer simulations, we study the dynamics of rigid monovalent cations (Li+, Na+, K+, and Cs+) in aqueous ethanol solutions with chloride as the counterion. We vary both the size of the ions and the composition of the mixture to explore size- and composition-dependent ion diffusion. The relative stability of enhanced microheterogeneous configurations makes ion diffusion slower than what would be surmised by using the bulk properties of the mixture, using the Stokes-Einstein relation. We study the structure through partial radial distribution functions and the stability through coordination number fluctuations. The ion diffusion coefficient exhibits sharp re-entrant behavior when plotted against viscosity varied by composition. Our studies reveal multiple anomalous features of ion motion in this mixture. We formulate a mode-coupling theory (MCT) that takes into account the interaction between different dynamical components; MCT can incorporate the effects of heterogeneous dynamics and nonlinearity in composition dependence that arise from the feedback between mutually dependent ion-solvent dynamics.