The double-layer structure of overscreened surfaces by smeared-out ions

Abstract

The present work focuses on the structure of a double-layer of overscreened charged surfaces by smeared-out charges and probes the link between the structure of a double-layer and the bulk properties of an electrolyte with special view to the role of the Kirkwood crossover. Just as the Kirkwood line divides a bulk solution into a fluid with monotonic and oscillatory decaying correlations, it similarly separates charge inversion into two broad domains, with and without oscillating charge density profile. As initially oscillations may appear like a far-field occurrence, eventually they develop into a full fledged layering of a charge density.

Describing screening in dense ionic fluids with a charge-frustrated Ising model

“…1 for ρQ/J = 0.5/a 2 . The analogy with gas and liquid-like correlations is useful intuitively (and has been noted by others in connection with the so-called Fisher-Widom line [7]), but one important difference here is that the oscillation frequency is not fixed by the ion size, and can instead vary significantly for different κ D (seeω given in Eq. 9).…”

“…In this large κ D regime, the charge correlation length can become much longer than the screening length predicted by DH theory, qualitatively similar to observations of anomalous screening in the aforementioned surface force experiments. More recent work based both on simulations and phenomenological theories reproduce this oscillatory, large κ D regime [3][4][5][6][7][8]. However, none of these theoretical studies reproduces the universal scaling reproduces in Ref.…”

On the equivalence of self-consistent equations for nonuniform liquids: a unified description of the various modifications

“…It is found from eqs. ( 36) and (37) that the introduction of smeared charge model is compatible with the use of the DCF in the liquid-state theory, as has been verified for the strongly coupled OCP (see Appendix A.5 for the details) [37,39,40]. Equations ( 37), ( 39) and ( 40) are reduced to eqs.…”

“…Our concern here is with the following two types of the modified PB equations. One type is derived from the charge smearing model [14,[20][21][22][23][24][35][36][37][38][39][40] and the other adds higher-order gradient terms to the original PB equation [15][16][17][18][25][26][27][28][29][30]. Both types of modifications have coexisted as complementary to each other, and the direct connections of these different types of the modified PB equations with the liquid-state theory, or the vast knowledge on correlation functions [1,41], remain to be clarified.…”

Mean-field theory of active electrolytes: Dynamic adsorption and overscreening

“…In recent years, the mean-field analysis has been extended to ions with inner structure to include an ever larger class of emerging systems. These extensions incorporate steric effects [6][7][8][9], multipolar interactions [10,11], polarizability [12,13], penetrability [14][15][16][17][18][19][20], nonspherical shapes such as that of dumbbell ions [21][22][23][24], and the various combinations of the above extensions [25].…”