Toward the Mechanism of Ionic Dissociation in Water

ABSTRACT: We investigate the solvent effects leading to dissociation of sodium chloride in water. Thermodynamic analysis reveals dissociation to be driven energetically and opposed entropically, with the loss in entropy due to an increasing number of solvent molecules entering the highly coordinated ionic solvation shell. We show through committor analysis that the ion−ion distance is an insufficient reaction coordinate, in agreement with previous findings. By application of committor analysis on various constrained solvent ensembles, we find that the dissociation event is generally sensitive to solvent fluctuations at long ranges, with both sterics and electrostatics of importance. The dynamics of the reaction reveal that solvent rearrangements leading to dissociation occur on time scales from 0.5 to 5 ps or longer, and that, near the transition state, inertial effects enhance the reaction probability of a given trajectory. Characterizing the dynamics of rare events is vital to the understanding of large-scale structural changes that occur i