Description beyond the mean-field approximation of an electrolyte confined between two planar metallic electrodes.
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/ W3 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 nonzero potential difference builds up between any electrode and the interior of the system although both electrodes are grounded.
Téllez
Gabriel
G
Departamento de Física, Universidad de Los Andes, A.A. 4976, Bogotá, Colombia. gtellez@uniandes.edu.co