Symmetry breaking and electrostatic attraction between two identical surfaces.
By allowing the surface charge of one surface to affect the adsorption equilibrium of the other, we establish the existence of a long-range attractive interaction between two identical surfaces in an electrolyte containing polyvalent counterions with a mean-field Poisson-Boltzmann approach. A Stern electrostatic condition from linearization of the mass-action adsorption isotherm is used to capture how polyvalent ion condensation affects and reverses the surface charge. We furthermore establish a direct mapping between this Stern-layer condition and previously derived modified mean-field formulations associated with correlated fluctuations theory. For a sufficiently potential-sensitive isotherm, antisymmetric charge inversion can occur to produce an attractive force that increases with decreasing ionic strengths. Analyses of a mass-action isotherm produce force-separation relations, including an exponential far-field force decay distinct but consistent with previously proposed correlated fluctuation theories and in quantitative agreement with experimental data.
Plouraboué
F
F
Université de Toulouse, INPT, UPS, Institut de Mécanique des Fluides de Toulouse, Allés Camille Soula, CNRS, IMFT, F-31400 Toulouse, France.
Chang
H-C
HC