This paper reports grand canonical Monte Carlo computations on the diffuse double layer in an ionic system next to a uniformly charged plane surface. The boundary conditions and the grand canonical techniques are discussed. Calculations were carried out for the 1:1 restricted primitive model at several concentrations and over a range of surface charge densities. The results are compared with the modified Gouyndash;Chapman theory, and some remarks are also possible with respect to the modified Poissonndash;Boltzmann and the hypernetted chain approaches. At high concentrations and surface charge densities the counterions are packed closely at the surface and begin to show a layered structure. This results in a large electrostatic potential drop, but only very slight charge oscillations are observed in the solution. None of the theories seems able to describe this behavior.
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