Local and Collective Reaction Coordinates in the Transport of the Aqueous Hydroxide Ion

Abstract

We investigate local and collective reaction coordinates for the structural diffusion of the hydroxide ion in dilute aqueous NaOH solution using a multistate empirical valence bond (MS-EVB) simulation. We characterize a 15 fs time scale associated with shifting of the equally shared proton within a Zundel-like H3O2(-) ion to form a water molecule, a 550 fs relaxation from this transition state largely guided by electrostatic fluctuations of the surrounding environment, and a 9.6 ps time scale that corresponds to the solvation of the water molecule formed by the proton transfer event. When individual proton transfer events are examined, we are unable to identify a unique transition state solely on the basis of a decrease in the hydroxide ion's coordination number. Instead, we find that the collective electric field along the proton transfer direction is better suited to describe the creation and relaxation of Zundel-like transition states that allow structural diffusion of the hydroxide ion.