Influence of electric-double-layer structure on the transient response of nanochannels.

A fundamental Poisson-Nernst-Planck-Stokes model is presented for the impedance response of a long nanochannel under zero bias, capturing the effects of surface conduction and the coupling between transverse momentum and axial ion distribution in a manner reminiscent of Taylor dispersion. This is shown to result in a shift of the impedance frequency spectrum with bulk concentration similar to previous experimental observation [Schiffbauer, Liel, and Yossifon, Phys. Rev. E 89, 033017 (2014)]. It further predicts an additional downward shift in frequency with increasing viscosity. Finally, the introduction of a phenomenological model for the impedance response of a dynamic Stern layer in parallel with the diffuse layer transport model is shown to yield good agreement between theory and experiment. As a result, we are able to obtain an equivalent circuit model based on the fundamental model and proposed corrections.