Applied Electric Field Effects on Diffusivity and Electrical Double-Layer Thickness.

ABSTRACT

This study utilizes molecular dynamics (MD) simulations and continuum frameworks to explore electroosmotic flow (EOF) in nanoconfined aqueous electrolytes, offering a promising alternative to conventional micro-/nanofluidic systems. Although osmotic behavior in these environments is deeply linked to local fluid properties and interfacial dynamics between the fluid and electrolyte solutions, achieving a complete molecular-level understanding has remained challenging. The findings establish a linear relationship between electric field strength and fluid velocity, uncovering two distinct transport regimes separated by a critical threshold, with a markedly intensified flow in the second regime. It is demonstrated that rising electric field strengths significantly enhance water diffusion coefficients, supported by a detailed analysis of fluid hydration structures, the potential of mean force (PMF), and local stress tensors. Due to the applied electric field strength, the motion of ions and water accelerates, leading to the redistribution of ions and intensification of electrostatic forces. This expands the thickness of the electric double layer (EDL) and amplifies fluid diffusivity, thereby enhancing nanoscale fluid activity. These insights enhance the molecular-level understanding of EOF and define the stability of flow regimes, providing valuable guidelines for advancing nanofluidic technologies, such as drug delivery systems and lab-on-a-chip devices.