Electrostatistics of counter-ions at and between planar charged walls: From Poisson-Boltzmann to the strong-coupling theory

Abstract:

The Poisson-Boltzmann (PB) approach gives asymptotically exact counter-ion density profiles around macroscopic charged objects and forces between macroscopic charged objects in the weak-coupling limit of low counter-ion valency, low surface-charge density, and high temperature. In this paper we derive, using field-theoretic methods, a theory which becomes exact in the opposite limit of strong coupling (SC). Formally, it corresponds to a standard virial expansion. Long-range divergences render the virial expansion intractable for homogeneous bulk systems, giving rise to non-analyticities in the low-density expansion of the free-energy density of electrolyte solutions. We demonstrate that for the case of inhomogeneous density distribution functions at macroscopic charged bodies these divergences are renormalizable by a systematic expansion in powers of the fugacity. For a single planar charged wall, we obtain the counter-ion density profile in the SC limit, which decays exponentially, in contrast to the PB result, which predicts algebraic decay, and in agreement with previously published numerical results. Similarly and highly charged plates in the presence of multivalent counter-ions attract each other in the SC limit and form electrostatically bound states, in contrast to the PB limit, where the interaction is always repulsive. By considering next-leading corrections to both the PB and SC theories, we estimate the range of validity for both theories.