Interaction confinement and electronic screening in two-dimensional nanofluidic channels.

The transport of fluids at the nanoscale is fundamental to manifold biological and industrial processes, ranging from neurotransmission to ultrafiltration. Yet, it is only recently that well-controlled channels with cross sections as small as a few molecular diameters became an experimental reality. When aqueous electrolytes are confined within such channels, the Coulomb interactions between the dissolved ions are reinforced due to dielectric contrast at the channel walls: We dub this effect "interaction confinement." Yet, no systematic way of computing these confined interactions has been proposed beyond the limiting cases of perfectly metallic or perfectly insulating channel walls. Here, we introduce a new formalism, based on the so-called surface response functions, that expresses the effective Coulomb interactions within a two-dimensional channel in terms of the wall's electronic structure, described to any desired level of precision. We use it to demonstrate that in few-nanometer-wide channels, the ionic interactions can be tuned by the wall material's screening length. We illustrate this approach by implementing these interactions in Brownian dynamics simulations of a strongly confined electrolyte and show that the resulting ionic conduction can be adjusted between Ohm's law and a Wien effect behavior. Our results provide a quantitative approach to tuning nanoscale ion transport through the electronic properties of the channel wall material.