Description beyond the mean field approximation of an electrolyte confined between two planar metallic electrodes

Abstract

We study an electrolyte confined in a slab of width $W$ composed of two grounded metallic parallel electrodes. We develop a description of this system in a low coupling regime beyond the mean field (Poisson--Boltzmann) approximation. There are two ways to model the metallic boundaries: as ideal conductors in which the electric potential is zero and it does not fluctuate, or as good conductors in which the average electric potential is zero but the thermal fluctuations of the potential are not zero. This latter model is more realistic. For the ideal conductor model we find that the disjoining pressure is positive behaves as $1/W^3$ for large separations with a prefactor that is universal, i.e. independent of the microscopic constitution of the system. For the good conductor boundaries the disjoining pressure is negative and it has an exponential decay for large $W$. We also compute the density and electric potential profiles inside the electrolyte. These are the same in both models. If the electrolyte is charge asymmetric we find that the system is not locally neutral and that a non-zero potential difference builds up between any electrode and the interior of the system although both electrodes are grounded.

16 pages, 5 figures, added a new appendix B and a discussion on ideal conductors vs. good conductors

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Cited by in corpus (4)

• Screening of classical Casimir forces by electrolytes in semi-infinite geometries
• Debye-Huckel theory for two-dimensional Coulomb systems living on a finite surface without boundaries
• General Considerations on the Finite-Size Corrections for Coulomb Systems in the Debye-Huckel Regime
• Poisson-Boltzmann Equation with a Random Field for Charged Fluids