Competition between Born solvation, dielectric exclusion, and Coulomb attraction in spherical nanopores

Phys Rev E. 2021 Oct;104(4-1):044601. doi: 10.1103/PhysRevE.104.044601.

Abstract

The recent measurement of a very low dielectric constant, ε, of water confined in nanometric slit pores leads us to reconsider the physical basis of ion partitioning into nanopores. For confined ions in chemical equilibrium with a bulk of dielectric constant ε_{b}>ε, three physical mechanisms, at the origin of ion exclusion in nanopores, are expected to be modified due to this dielectric mismatch: dielectric exclusion at the water-pore interface (with membrane dielectric constant, ε_{m}<ε), the solvation energy related to the difference in Debye-Hückel screening parameters in the pore, κ, and in the bulk κ_{b}, and the classical Born solvation self-energy proportional to ε^{-1}-ε_{b}^{-1}. Our goal is to clarify the interplay between these three mechanisms and investigate the role played by the Born contribution in ionic liquid-vapor (LV) phase separation in confined geometries. We first compute analytically the potential of mean force (PMF) of an ion of radius R_{i} located at the center of a nanometric spherical pore of radius R. Computing the variational grand potential for a solution of confined ions, we then deduce the partition coefficients of ions in the pore versus R and the bulk electrolyte concentration ρ_{b}. We show how the ionic LV transition, directly induced by the abrupt change of the dielectric contribution of the PMF with κ, is favored by the Born self-energy and explore the decrease of the concentration in the pore with ε both in the vapor and liquid states. Phase diagrams are established for various parameter values and we show that a signature of this phase transition can be detected by monitoring the total osmotic pressure as a function of R. For charged nanopores, these exclusion effects compete with the electrostatic attraction that imposes the entry of counterions into the pore to enforce electroneutrality. This study will therefore help in deciphering the respective roles of the Born self-energy and dielectric mismatch in experiments and simulations of ionic transport through nanopores.