Revealing the Anticorrelation Behavior Mechanism between the Grotthuss and Vehicular Diffusions for Proton Transport in Concentrated Acid Solutions

In this study, we performed reactive molecular dynamics simulations to characterize proton solvation and transport in concentrated hydrochloric acid solutions. The correlation contribution to the total proton mean square displacement is found to be negative for all acid concentrations, indicating the anticorrelation between the Grotthuss and vehicular diffusions. For the vehicular diffusion, the hydronium ions tend to move freely toward the lone pair side independent of acid concentrations, whereas for the Grotthuss diffusion, the proton hopping direction is limited to one of the hydrogen-bonded water molecules on the opposite side of the lone pair region, which are specifically oriented with respect to the neighboring hydronium ion at higher acid concentrations. This result is justified by our findings of the higher fraction of proton rattling with the single hopping event and longer hydrogen bond lifetimes at higher acid concentrations. However, the angular distribution for both the vehicular and Grotthuss diffusions is found to be rather broad and comparable for all acid concentrations, and thus, the anticorrelation shows a minimal dependence on the acid concentration. Our results reveal that the anticorrelation behavior between the vehicle and Grotthuss diffusions is attributed to the amphiphilic nature of hydronium ions and thus is independent of the acid concentrations in solutions.