We perform atomistic simulations of nanometer-separated charged surfaces in the presence of monovalent counterions at fixed water chemical potential. The counterion density profiles are well described by a modified Poisson–Boltzmann (MPB) approach that accounts for nonelectrostatic ion–surface interactions, while the effects of smeared-out surface-charge distributions and dielectric profiles are found to be relatively unimportant. The simulated surface interactions are for weakly charged surfaces well described by the additive contributions of hydration and MPB repulsions, but already for a moderate surface charge density of σ = −0.77 e/nm2 this additivity breaks down. This we rationalize by a combination of different effects, namely, counterion correlations as well as the surface charge-induced reorientation of hydration water, which modifies the effective water dielectric constant as well as the hydration repulsion.
