Impedance of nanocapacitors from molecular simulations to understand the dynamics of confined electrolytes

Nanoelectrochemical devices have become a promising candidate technology across various applications, including sensing and energy storage, and provide new platforms for studying fundamental properties of electrode/electrolyte interfaces. In this work, we employ constant-potential molecular dynamics simulations to investigate the impedance of gold-aqueous electrolyte nanocapacitors, exploiting a recently-introduced fluctuation-dissipation relation. In particular, we relate the frequency-dependent impedance of these nanocapacitors to the complex conductivity of the bulk electrolyte in different regimes, and use this connection to design simple but accurate equivalent circuit models. We show that the electrode/electrolyte interfacial contribution is essentially capacitive and that the electrolyte response is bulk-like even when the interelectrode distance is only of a few nanometers, provided that the latter is sufficiently large compared to the Debye screening length. We extensively compare our simulation results with spectroscopy experiments and predictions from analytical theories. This work opens new avenues for the molecular interpretation of impedance measurements, and offers valuable contributions for future developments of accurate coarse-grained representations of confined electrolytes.