Effective Electrostatic Interactions Between Two Overall Neutral Surfaces with Quenched Charge Heterogeneity Over Atomic Length Scale

Using Monte Carlo results as a reference, a classical density functional theory ( CDFT ) is shown to reliably predict the forces between two heterogeneously charged surfaces immersed in an electrolyte solution, whereas the Poisson–Boltzmann ( PB ) theory is demonstrated to deteriorate obviously for the same system even if the system parameters considered fall within the validity range of the PB theory in the homogeneously charged surfaces. By applying the tested CDFT , we study the effective electrostatic potential of mean force ( EPMF ) between two face–face planar and hard surfaces of zero net charge on which positive and negative charges are separated and considered to present as discontinuous spots on the inside edges of the two surfaces. Main conclusions are summarized as follows: (i) strength of the EPMF in the surface charge separation case is very sensitively and positively correlated with the surface charge separation level and valency of the salt ion. Particularly, the charge separation level and the salt ion valency have a synergistic effect, which makes high limit of the EPMF strength in the surface charge separation case significantly go beyond that of the ideal homogeneously charged surface counterpart at average surface charge density similar to the average surface positive or negative charge density in the charge separation case. (ii) The surface charge distribution patterns mainly influence sign of the EPMF : symmetrical and asymmetrical patterns induce repulsive and attractive (at small distances) EPMF , respectively; but with low valency salt ions and low charge separation level the opposite may be the case. With simultaneous presence of both higher valency cation and anion, the EPMF can be repulsive at intermediate distances for asymmetrical patterns. (iii) Salt ion size has a significant impact, which makes the EPMF tend to become more and more repulsive with the ion diameter regardless of the surface charge distribution patterns and the valency of the salt ion; whereas if the 1:1 type electrolyte and the symmetrical patterns are considered, then the opposite may be the case. All of these findings can be explained self-consistently from several perspectives: an excess adsorption of the salt ions (induced by the surface charge separation) serving to raise the osmotic pressure between the plates, configuration fine-tuning in the thinner ion adsorption layer driven by the energy decrease principle, direct Coulombic interactions operating