Hydrodynamic Interactions in Ion Transport -- Theory and Simulation

TL;DR

This paper develops a hydrodynamic theory for ion pair diffusion in periodic systems, compares it with molecular dynamics simulations of electrolytes and ionic liquids, and discusses implications for ion conductivity and finite-size effects.

Contribution

It generalizes previous self-diffusion models to pair diffusion, providing a theoretical framework validated by simulations for complex ionic systems.

Findings

Good agreement between theory and simulations on ion correlations.

Hydrodynamic interactions largely cancel in total conductivity contributions.

Deviations from ideal fluid flow influence conductivity through local structure and relaxation.

Abstract

We present a hydrodynamic theory describing pair diffusion in systems with periodic boundary conditions, thereby generalizing earlier work on self-diffusion [D\"unweg and Kremer, J. Chem. Phys. 1993, 99, 6983-6997; Yeh and Hummer, J. Phys. Chem. B 2004, 108, 15873-15879]. Its predictions are compared to Molecular Dynamics simulations for a liquid carbonate electrolyte and two ionic liquids, for which we characterize the correlated motion between distinct ions. Overall, we observe good agreement between theory and simulation data, highlighting that hydrodynamic interactions universally dictate ion correlations. However, when summing over all ion pairs in the system to obtain the cross-contributions to the total cationic or anionic conductivity, the hydrodynamic interactions between ions with like and unlike charges largely cancel. Consequently, significant conductivity contributions only arise from deviations from a hydrodynamic flow field of an ideal fluid, that is, from the local electrolyte structure as well as from relaxation processes in the subdiffusive regime. In case of ionic liquids, the momentum-conservation constraint additionally is vital, which we study by employing different ionic masses in the simulations. Our formalism will likely also be helpful to estimate finite-size effects of the conductivity or of Maxwell-Stefan diffusivities in simulations.