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

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.

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Cited by in corpus (5)

• Equivalent circuit and continuum modeling of the impedance of electrolyte-filled pores
• Constant Potential and Constrained Charge Ensembles for Simulations of Conductive Electrodes
• Interfacial Thermal Transport and Electrical Performance of Supercapacitors with Graphene/Carbon Nanotube Composite Electrodes
• Hyperballistic transport in dense systems of charged particles under ac electric fields
• Brownian dynamics simulations of electric double-layer capacitors with tunable metallicity