Macroscopic conductivity of aqueous electrolyte solutions scales with ultrafast 
microscopic ion motions

Balos, Vasileios; Imoto, Sho; Netz, Roland R.; Bonn, Mischa; Bonthuis, Douwe Jan; Nagata, Yuki; Hunger, Johannes

doi:10.1038/s41467-020-15450-2

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Macroscopic conductivity of aqueous electrolyte solutions scales with ultrafast microscopic ion motions

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Balos, Vasileios
Physical Chemistry, Fritz Haber Institute, Max Planck Society;
Department of Molecular Spectroscopy, Max Planck Institute for Polymer Research;

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Citation

Balos, V., Imoto, S., Netz, R. R., Bonn, M., Bonthuis, D. J., Nagata, Y., et al. (2020). Macroscopic conductivity of aqueous electrolyte solutions scales with ultrafast microscopic ion motions. Nature Communications, 11: 1611. doi:10.1038/s41467-020-15450-2.

Cite as: https://hdl.handle.net/21.11116/0000-0006-39C4-D

Abstract

Despite the widespread use of aqueous electrolytes as conductors, the molecular mechanism of ionic conductivity at moderate to high electrolyte concentrations remains largely unresolved. Using a combination of dielectric spectroscopy and molecular dynamics simulations, we show that the absorption of electrolytes at ~0.3 THz sensitively reports on the local environment of ions. The magnitude of these high-frequency ionic motions scales linearly with conductivity for a wide range of ions and concentrations. This scaling is rationalized within a harmonic oscillator model based on the potential of mean force extracted from simulations. Our results thus suggest that long-ranged ionic transport is intimately related to the local energy landscape and to the friction for short-ranged ion dynamics: a high macroscopic electrolyte conductivity is thereby shown to be related to large-amplitude motions at a molecular scale.