Nonlinear screening and effective electrostatic interactions in charge-stabilized colloidal suspensions

Abstract

A nonlinear response theory is developed and applied to electrostatic interactions between spherical macroions, screened by surrounding microions, in charge-stabilized colloidal suspensions. The theory describes leading-order nonlinear response of the microions (counterions, salt ions) to the electrostatic potential of the macroions and predicts microion-induced effective many-body interactions between macroions. A linear response approximation [A.R. Denton, Phys. Rev. E 62, 3855 (2000)] yields an effective pair potential of screened-Coulomb (Yukawa) form, as well as a one-body volume energy, which contributes to the free energy. Nonlinear response generates effective many-body interactions and essential corrections to both the effective pair potential and the volume energy. By adopting a random-phase approximation (RPA) for the response functions, and thus neglecting microion correlations, practical expressions are derived for the effective pair and triplet potentials and for the volume energy. Nonlinear screening is found to weaken repulsive pair interactions, induce attractive triplet interactions, and modify the volume energy. Numerical results for monovalent microions are in good agreement with available ab initio simulation data and demonstrate that nonlinear effects grow with increasing macroion charge and concentration and with decreasing salt concentration. In the dilute limit of zero macroion concentration, leading-order nonlinear corrections vanish. Finally, it is shown that nonlinear response theory, when combined with the RPA, is formally equivalent to the mean-field Poisson-Boltzmann theory and that the linear response approximation corresponds, within integral-equation theory, to a linearized hypernetted-chain closure.