Electrochimica Acta, Vol.43, No.12-13, 1931-1938, 1998
Dipole interactions at the electrode/electrolyte interface including a short-range correlation effect
Intermolecular dipole-dipole interactions between solvent molecules adsorbed on the electrode surface are considered. Description of the interactions is based on the extension of the mean molecular field by a contribution due to a short-range correlation effect. It is assumed that a given molecule changes orientation of its nearest neighbours through the fluctuation field. The field acting on the molecule is the sum of the mean field and the field due to that change in the orientation. The calculated mean electric dipole moment, the differential dipolar polarizability and the mean energy of intermolecular interactions are close to the corresponding results obtained from the Monte Carlo simulation. The dipolar polarizabilities are additionally compared with the corresponding results basing on the mean molecular field approximation. The differential capacity of the inner layer is calculated from the dipolar polarizability. For strong intermolecular interactions, the differential capacity still exhibits the polarization catastrophe although its intensity is reduced.