Wigner-crystal formulation of strong-coupling theory for counterions near planar charged interfaces
Ladislav Samaj1, Emmanuel Trizac
1Laboratoire de Physique Théorique et Modèles Statistiques, UMR CNRS 8626, Université Paris-Sud, F-91405 Orsay, France.
Abstract:
We present a new analytical approach to the strong electrostatic coupling regime (SC) that can be achieved equivalently at low temperatures, high charges, low dielectric permittivity, etc. Two geometries are analyzed in detail: one charged wall first, and then two parallel walls at small distances that can be likely or oppositely charged. In all cases, only one type of mobile counterions is present, and ensures electroneutrality (salt-free case). The method is based on a systematic expansion around the ground state formed by the two-dimensional Wigner crystal(s) of counterions at the plate(s). The leading SC order stems from a single-particle theory, and coincides with the virial SC approach that has been much studied in the last 10 years. The first correction has the functional form of the virial SC prediction, but the prefactor is different. The present theory is free of divergences and the obtained results, both for symmetrically and asymmetrically charged plates, are in excellent agreement with available data of Monte Carlo simulations under strong and intermediate Coulombic couplings. All results obtained represent relevant improvements over the virial SC estimates. The present SC theory starting from the Wigner crystal and therefore coined Wigner SC, sheds light on anomalous phenomena like the counterion mediated like-charge attraction, and the opposite-charge repulsion.
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