A strong-coupling effective-field theory for asymmetrically charged plates with counterions only

TL;DR

This paper extends an effective-field theory to asymmetric charged plates with counterions, accurately predicting attractive forces and ion sharing behavior in strong coupling regimes, validated by Monte Carlo simulations.

Contribution

It generalizes the effective-field theory to asymmetric plates, introducing a variational counterion occupation parameter to describe ion sharing and attraction.

Findings

Analytical pressure results match Monte Carlo data across coupling regimes.

Existence of a $1/d^2$ attractive pressure at large distances.

Ion sharing depends on coupling strength and plate separation.

Abstract

We are interested in rationalizing the phenomenon of like-charge attraction between charged bodies, such as a pair of colloids, in the strong coupling regime. The two colloids are modelled as uniformly charged parallel plates, neutralized by mobile counterions. In an earlier work [Palaia et al., J. Phys. Chem. B 126, 3143 (2022)], we developed an effective-field theory for symmetric plates, stemming from the ground-state description that holds at infinite couplings. Here, we generalize the approach to the asymmetric case, where the plates bear charges of the same sign, but of different values. In the symmetric situation, the mobile ions, which are localized in the vicinity of the two plates, share equally between both of them. Here, the sharing is non-trivial, depending both on the coupling parameter and the distance between the plates. We thus introduce a counterion occupation parameter, that is determined variationally to ensure minimum of the free energy. The resulting analytical results for the pressure as a function of the plate-plate distance $d$ agree well with our Monte Carlo data, in a large interval of strong and intermediate coupling constants $\Xi$. We show in particular that within this description, there exists a range of large distances at which the attractive pressure features a $1/d^2$ behavior.