NONLINEAR POISSON-BOLTZMANN THEORY OF A DOUBLE-LAYER AT A ROUGH METALELECTROLYTE INTERFACE - A NEW LOOK AT THE CAPACITANCE DATA ON SOLID ELECTRODES/

Nonlinear Poisson-Boltzmann theory is developed to extend our previous work [Phys. Rev. E 53, 6192 (1996)] on the case when the potential dr op across the double layer is not small compared to the thermal energy . Close to the potentials of zero charge (pzc) the effect of surface r oughness on the double-layer capacitance is mainly determined by an in terplay between the lateral correlation length of roughness and the De bye length. However, far from the pzc dramatic effects of electrode po tential are found which are not reduced to the potential-induced short ening of the diffuse layer thickness. (C) 1998 American Institute of P hysics. [S0021-9606(98)51204-4].