Electrical Conductivity Differences between Experiments and Classical Simulations Reveal Self-Diffusion Coefficients...

Grotthuss transfer is responsible for a large increase in the self-diffusion of hydroxide and hydronium ions in aqueous solutions compared to similarly sized ions. Recent advances in machine-learning molecular dynamics have shown some success in capturing this process. In the present work, we show that classical molecular dynamics combined with experimentally measured electrical conductivities can also be used to determine self-diffusion coefficients and the lifetimes of hydroxide and hydronium ions in aqueous KOH, NaOH, and HCl solutions. This was tested and validated across a wide range of concentrations at 25 and 60 °C. The approach relies on augmenting classically computed trajectories with a biased random walk, which together accounts for both vehicular transport and Grotthuss transfer. The concentration and temperature dependence of this random walk are calibrated by comparing simulated electrical conductivities with available experimental electrical conductivity data. The computed self-diffusion coefficients match measurements at infinite dilution and results from machine learning molecular dynamics. Ion lifetimes reported by machine learning and ab initio molecular dynamics studies depend strongly on the precise definition of what constitutes a Grotthuss transfer event. Our approach for calculating ion lifetimes does not have this drawback. We also show that our self-diffusion coefficients and electrical conductivities are insensitive to the precise definition of what constitutes a Grotthuss transfer event.