Frequency-dependent impedance of nanocapacitors from electrode charge fluctuations as a probe of electrolyte dynamics

TL;DR

This paper introduces a method to determine the frequency-dependent impedance of nanocapacitors from equilibrium charge fluctuations in simulations, linking microscopic electrolyte dynamics to measurable electrochemical properties.

Contribution

It extends fluctuation-dissipation theory to capacitance and demonstrates how to interpret impedance measurements through microscopic electrolyte dynamics.

Findings

Impedance can be derived from charge fluctuations in simulations.

Method applied to water/gold nanocapacitors.

Facilitates microscopic understanding of electrochemical impedance.

Abstract

The frequency-dependent impedance is a fundamental property of electrical components. We show that it can be determined from the equilibrium dynamical fluctuations of the electrode charge in constant-potential molecular simulations, extending in particular a fluctuation-dissipation for the capacitance recovered in the low-frequency limit and provide an illustration on water/gold nanocapacitors. This work opens the way to the interpretation of electrochemical impedance measurements in terms of microscopic mechanisms, directly from the dynamics of the electrolyte, or indirectly via equivalent circuit models as in experiments.