Exponential Scaling of Water Exchange Rates with Ion Interaction Strength from the Perspective of Dynamic Facilitation Theory.

Abstract

Water exchange reactions around ionic solutes are ubiquitous in aqueous solution-phase chemistry. However, the extreme sensitivity of exchange rates to perturbations in the chemistry of an ionic solute is not well understood. We examine water exchange around model ions within the language of dynamic facilitation theory, typically used to describe glassy and other systems with collective, facilitated dynamics. Through the development of a coarse-grained, kinetically constrained lattice model of water exchange, we show that the time scale for water exchange scales exponentially with the strength of the solute-solvent interactions.