Energetics of counterion adsorption in the electrical double layer

The energetics of the electrical double layer (EDL) is studied in a systematic way to define how different components of the chemical potential help or hinder cation adsorption at a negatively charged wall. Specifically, the steric (i.e., excluded-volume interactions), mean electrostatic, and screening (i.e., electrostatic correlations beyond the mean field) components were computed using classical density functional theory of the primitive model of ions (i.e., ions as charged, hard spheres in a background dielectric). The reduced physics of the primitive model allows for an extensive analysis over a large parameter space: cation valences +1, +2, and +3, cation diameters 0.15, 0.30, 0.60, and 0.90 nm, bulk concentrations ranging from 1 µM to 1M, and surface charges ranging from 0 to -0.50 C/m². Our results show that all components are necessary to understand the physics of the EDL. The screening component is always significant; for small monovalent cations such as K⁺, it is generally much larger than the steric component, and for multivalent ions, charge inversion cannot occur without it. At moderate surface charges, the screening component makes the electrostatic potential less negative than in classical Poisson-Boltzmann theory, sometimes even positive (charge inversion). At high surface charges, this is overcome by the repulsive potential of the steric component as the first ion layer becomes extremely crowded. Large negative electrostatic potentials counteract this to draw even more cations into the first layer. Although we used an approximate model of the EDL, the physics inherent in these trends appears to be quite general.