Hydrodynamic interactions in ion transport-Theory and simulation. 2023

Diddo Diddens, and Andreas Heuer
Helmholtz Institute Münster: Ionics in Energy Storage (IEK-12), Forschungszentrum Jülich GmbH, Corrensstraße 46, 48149 Münster, Germany.

We present a hydrodynamic theory describing pair diffusion in systems with periodic boundary conditions, thereby generalizing earlier work on self-diffusion [B. Dünweg and K. Kremer, J. Chem. Phys. 99, 6983-6997 (1993) and I.-C. Yeh and G. Hummer, J. Phys. Chem. B 108, 15873-15879 (2004)]. Its predictions are compared with 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, which is from the local electrolyte structure as well as the relaxation processes in the subdiffusive regime. In the 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.

UI MeSH Term Description Entries

Related Publications

Diddo Diddens, and Andreas Heuer
February 1996, Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics,
Diddo Diddens, and Andreas Heuer
September 1995, Physical review. D, Particles and fields,
Diddo Diddens, and Andreas Heuer
June 2018, Journal of colloid and interface science,
Diddo Diddens, and Andreas Heuer
March 2005, Physical review. E, Statistical, nonlinear, and soft matter physics,
Diddo Diddens, and Andreas Heuer
June 2014, The Journal of chemical physics,
Diddo Diddens, and Andreas Heuer
January 1996, Advances in space research : the official journal of the Committee on Space Research (COSPAR),
Diddo Diddens, and Andreas Heuer
April 2013, Physical review. E, Statistical, nonlinear, and soft matter physics,
Diddo Diddens, and Andreas Heuer
August 2016, Proceedings of the National Academy of Sciences of the United States of America,
Diddo Diddens, and Andreas Heuer
August 1978, Journal of theoretical biology,
Diddo Diddens, and Andreas Heuer
December 1989, Physical review. A, General physics,
Copied contents to your clipboard!