Dipolar solvent contributions for transient nanoscale electroosmotic flow

TL;DR

This paper develops a continuum model incorporating dipolar solvent effects, such as dielectric saturation and viscoelectricity, to accurately describe transient electroosmotic flows at the nanoscale, revealing significant deviations from traditional models.

Contribution

It introduces a novel solvent-consistent PNP-S framework that accounts for molecular solvent structure effects on electroosmotic flow evolution at the nanoscale.

Findings

Electroosmotic mobility can decrease by up to 50% due to solvent effects.

Dipolar solvent physics significantly alter electrohydrodynamic body forces.

Transient flow behavior departs from constant-permittivity and viscosity assumptions.

Abstract

Electrohydrodynamic flows of weak electrolytes at the nanoscale are significantly influenced by the molecular structure of water-like polar solvents within the electric double layer (EDL). Moreover, unlike in microfluidics, at these length scales the time scale of evolution of EDL often becomes comparable to the consequent fluidic phenomena of interest. While continuum descriptions to model such phenomena typically assume a constant dielectric and viscous solvent background, this study incorporates dipolar solvent physics, specifically both dielectric saturation and the viscoelectric effect together, into a Poisson-Nernst-Planck-Stokes (PNP-S) framework, using the Langevin-Bikerman solvent permittivity distribution and empirical viscoelectric coefficients, respectively. Numerical simulations in a one-dimensional geometry reveal substantial modifications to the electrohydrodynamic body force density and transient electroosmotic mobility during EDL evolution. The magnitude and temporal evolution of these corrections are characterized across parametric regimes, revealing systematic departures from standard constant-permittivity and constant-viscosity models, with electroosmotic mobility reductions of up to 50% governed by a characteristic dimensionless parameter. The results provide a solvent-consistent continuum framework for transient nanoscale electroosmotic flows and quantify the impact of molecular solvent structure on electrohydrodynamic transport relevant to modern nanofluidic applications.