Surface Charge Doping for Ion-Pairing Criticality in Confined Electrolytes

Abstract

Dielectric confinement strengthens Coulomb correlations in quasi-two-dimensional electrolytes and can promote Bjerrum pairing in charge-neutral slits. Here we use a generalized Debye-Huckel-Bjerrum theory to show that weak surface charge changes this picture by stoichiometrically doping the slit with mobile counterions. These counterions maintain a finite screening floor, decouple microscopic pairing from macroscopic ionicity, and shift association-driven criticality to lower temperatures. The critical-temperature suppression collapses onto a single scaled perturbation variable, revealing how surface charge and dielectric confinement jointly control charged nanofluidic slits. Brownian-dynamics tests further show that the same counterions are not always fully bulk-like diffusive: at low intrinsic salt density, explicit wall charge slows in-plane diffusion, whereas at higher intrinsic density the wall-induced diffusion penalty decreases and the mobile-counterion description becomes dynamically accurate. These results identify surface charge as a thermodynamic doping field that tunes both correlated ionic stability and the diffusion mechanism in nanofluidic confinement.