Molecular Origins of the Barriers to Proton Transport in Acidic Aqueous Solutions

The self-consistent iterative multistate empirical valence bond (SCI-MS-EVB) method is used to analyze the structure, thermodynamics, and dynamics of hydrochloric acid solutions. The reorientation time scales of irreversible proton transport are elucidated by simulating 0.43, 0.85, 1.68, and 3.26 M HCl solutions at 270, 285, 300, 315, and 330 K. The results indicate increased counterion pairing with increasing concentration, which manifests itself via a reduced hydronium oxygen–chloride (O*–Cl) structuring in the radial distribution functions. Increasing ionic concentration also reduces the diffusion of the hydrated excess protons, principally by reducing the contribution of the Grotthuss proton hopping (shuttling) mechanism to the overall diffusion process. In agreement with prior experimental findings, a decrease in the activation energy of reorientation time scales was also observed, which is explicitly explained by using activated rate theory and an energy–entropy decomposition of the state-averaged radial distribution functions. These results provide atomistic verification of suggestions from recent two-dimensional infrared spectroscopy experiments that chloride anions (as opposed to hydrated excess protons) create entropic barriers to proton transport.