Violation of the electroneutrality condition in confined unsymmetrical electrolytes

Fluid–Fluid Correlation through a Model Charged Membrane: Analytical Results

“…The violation to the LEC means that the induced charge in the fluid at both sides of the plate does not cancel the charge of the corresponding wall, although a general electroneutrality condition (GEC) is always satisfied; that is, the sum of the induced charge in the fluid at both sides of the plate cancel the total superficial charge density. This theory was also applied to confined systems by two plates and by a spherical nanopore, obtaining similar results (32)(33)(34), which are in very good agreement with Monte Carlo (MC) simulations (19,34,35). A shortcoming of these approaches, however, is that they require sophisticated numerical solutions.…”

Charge neutrality breakdown in confined aqueous electrolytes: Theory and simulation

“…Instead we will explore the role that electrostatic correlations 1 play in charge neutrality breakdown. A similar line of investigation has been taken by Lozada-Cassou and co-workers 46,47 , who used a three-point extended version of the traditional IE formalism to address the problem of electroneutrality violation in electrolytes confined by parallel charged surfaces. In this approach, the two-plate system was modeled as "dumbbell-like" molecules at infinite dilution, and the resulting ionic profiles were calculated as thee-body wall-wall-ion correlations [29][30][31][32][60][61][62] .…”

“…[46] and [47]. We will also investigate to what extent the absence of electroneutrality between the confining plates influences the net forces between the charged surfaces.…”

“…In order to avoid any confusion, we emphasize that from now on the term charge neutrality will refer to the local electroneutrality of electrolyte confined between charged walls. The possibility that electrolytes in contact with a bulk reservoir might lack charge neutrality in situations of strong confinement has been already discussed both theoretically 46,47 and observed in computer simulations [48][49][50] . However, these findings have only very recently been confirmed experimentally in the work of Luo et al 51 , who demonstrated that electrolytes confined in narrow pores do not in general exhibit electroneutrality.…”

Macroion−Macroion Correlations in Presence of Divalent Counterions

“…23 The HNC approximation consists of two equations. One is the Ornstein-Zernike equation, which correlates the total correlation function, h ij (12) ) g ij (12) -1, and the direct correlation function, c ij (12) 24 where F k is the number density of the component k. The second equation is given by 24…”