Frequency-Dependent Impedance of Nanocapacitors from Electrode Charge Fluctuations as a Probe of Electrolyte Dynamics
Giovanni Pireddu, Benjamin Rotenberg
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 relation for the capacitance recovered in the low-frequency limit and provide an illustration on water-gold nanocapacitors. This Letter 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.
Topics & Concepts
ElectrolyteElectrical impedanceCapacitanceElectrodeMaterials scienceChemical physicsDissipationLow frequencyDielectric spectroscopyEquivalent circuitElectrochemistryPhysicsCondensed matter physicsThermodynamicsVoltageQuantum mechanicsAstronomyElectrochemical Analysis and ApplicationsNanopore and Nanochannel Transport StudiesFuel Cells and Related Materials