Ionic screening in bulk and under confinement

Abstract

Recent experiments have shown that the repulsive force between atomically flat, like-charged surfaces confining room-temperature ionic liquids or concentrated electrolytes exhibits an anomalously large decay length. In our previous publication [J. Zeman, S. Kondrat, and C. Holm, Chem. Commun. 56, 15635 (2020)], we showed by means of extremely large-scale molecular dynamics simulations that this so-called underscreening effect might not be a feature of bulk electrolytes. Herein, we corroborate these findings by providing additional results with more detailed analyses and expand our investigations to ionic liquids under confinement. Unlike in bulk systems, where screening lengths are computed from the decay of interionic potentials of mean force, we extract such data in confined systems from cumulative charge distributions. At high concentrations, our simulations show increasing screening lengths with increasing electrolyte concentration, consistent with classical liquid state theories. However, our analyses demonstrate that - also for confined systems - there is no anomalously large screening length. As expected, the screening lengths determined for ionic liquids under confinement are in good quantitative agreement with the screening lengths of the same ionic systems in bulk. In addition, we show that some theoretical models used in the literature to relate the measured screening lengths to other observables are inapplicable to highly concentrated electrolytes.