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

Author

Listed:
  • Vasileios Balos

    (Max Planck Institute for Polymer Research
    Fritz Haber Institute of the Max Planck Society)

  • Sho Imoto

    (Max Planck Institute for Polymer Research)

  • Roland R. Netz

    (Freie Universität Berlin)

  • Mischa Bonn

    (Max Planck Institute for Polymer Research)

  • Douwe Jan Bonthuis

    (Freie Universität Berlin
    Graz University of Technology)

  • Yuki Nagata

    (Max Planck Institute for Polymer Research)

  • Johannes Hunger

    (Max Planck Institute for Polymer Research)

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.

Suggested Citation

  • Vasileios Balos & Sho Imoto & Roland R. Netz & Mischa Bonn & Douwe Jan Bonthuis & Yuki Nagata & Johannes Hunger, 2020. "Macroscopic conductivity of aqueous electrolyte solutions scales with ultrafast microscopic ion motions," Nature Communications, Nature, vol. 11(1), pages 1-8, December.
    • Handle: RePEc:nat:natcom:v:11:y:2020:i:1:d:10.1038_s41467-020-15450-2
    DOI: 10.1038/s41467-020-15450-2
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    Cited by:

    1. Florian N. Brünig & Manuel Rammler & Ellen M. Adams & Martina Havenith & Roland R. Netz, 2022. "Spectral signatures of excess-proton waiting and transfer-path dynamics in aqueous hydrochloric acid solutions," Nature Communications, Nature, vol. 13(1), pages 1-12, December.
    2. Iurii Chubak & Leeor Alon & Emilia V. Silletta & Guillaume Madelin & Alexej Jerschow & Benjamin Rotenberg, 2023. "Quadrupolar 23Na+ NMR relaxation as a probe of subpicosecond collective dynamics in aqueous electrolyte solutions," Nature Communications, Nature, vol. 14(1), pages 1-10, December.

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