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@ARTICLE{Diddens:1015192,
author = {Diddens, Diddo and Heuer, Andreas},
title = {{H}ydrodynamic interactions in ion transport—{T}heory and
simulation},
journal = {The journal of chemical physics},
volume = {158},
number = {15},
issn = {0021-9606},
address = {Melville, NY},
publisher = {American Institute of Physics},
reportid = {FZJ-2023-03588},
pages = {154112},
year = {2023},
abstract = {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.},
cin = {IEK-12},
ddc = {530},
cid = {I:(DE-Juel1)IEK-12-20141217},
pnm = {1221 - Fundamentals and Materials (POF4-122)},
pid = {G:(DE-HGF)POF4-1221},
typ = {PUB:(DE-HGF)16},
UT = {WOS:001010650400005},
doi = {10.1063/5.0147339},
url = {https://juser.fz-juelich.de/record/1015192},
}