Adsorption and Depletion of Polyelectrolytes from Charged Surfaces

Mean-field theory and scaling arguments are presented to model polyelectrolyte adsorption from semi-dilute solutions onto charged surfaces. Using numerical solutions of the mean-field equations, we show that adsorption exists only for highly charged polyelectrolytes in low salt solutions. Simple scaling laws for the width of the adsorbed layer and the amount of adsorbed polyelectrolyte are obtained. In other situations the polyelectrolyte chains will deplete from the surface. For fixed surface potential conditions, the salt concentration at the adsorption--depletion crossover scales as the product of the charged fraction of the polyelectrolyte f and the surface potential, while for a fixed surface charge density, \sigma, it scales as \sigma^{2/3}f^{2/3}, in agreement with single-chain results.Comment: 12 pages, 8 figures, final version to be published in J. Chem. Phys. 200

Surface induced ordering in thin film diblock copolymers: tilted lamellar phases

We investigate the effect of chemically patterned surfaces on the morphology of diblock copolymers below the order-disorder transition. Profiles for lamellar phases in contact with one surface, or confined between two surfaces are obtained in the weak segregation limit using a Ginzburg-Landau expansion of the free energy, and treating it with mean-field theory. The periodically patterned surface induces a tilt of the lamellae in order to match the surface periodicity. The lamellae relax from the constrained periodicity close to the surface to the bulk periodicity far from it. The phases we investigate are a generalization to the mixed (perpendicular and parallel to the surface) lamellar phases occurring when the two surfaces are homogeneous. A special case when the surface pattern has a period equal to the bulk lamellar period showing ``T-junction'' morphology is examined. Our analytic calculation agrees with previous computer simulations and self consistent field theories.Comment: 7 figures, replaced with minor modification

Wigner-Crystal Formulation of Strong-Coupling Theory for Counter-ions Near Planar Charged Interfaces

We present a new analytical approach to the strong electrostatic coupling regime (SC), that can be achieved equivalently at low temperatures, high charges, low dielectric permittivity etc. Two geometries are analyzed in detail: one charged wall first, and then, two parallel walls at small distances, that can be likely or oppositely charged. In all cases, one type of mobile counter-ions only is present, and ensures electroneutrality (salt free case). The method is based on a systematic expansion around the ground state formed by the two-dimensional Wigner crystal(s) of counter-ions at the plate(s). The leading SC order stems from a single-particle theory, and coincides with the virial SC approach that has been much studied in the last 10 years. The first correction has the functional form of the virial SC prediction, but the prefactor is different. The present theory is free of divergences and the obtained results, both for symmetrically and asymmetrically charged plates, are in excellent agreement with available data of Monte-Carlo simulations under strong and intermediate Coulombic couplings. All results obtained represent relevant improvements over the virial SC estimates. The present SC theory starting from the Wigner crystal and therefore coined Wigner SC, sheds light on anomalous phenomena like the counter-ion mediated like-charge attraction, and the opposite-charge repulsion

Electrostatic Disorder-Induced Interactions in Inhomogeneous Dielectrics

We investigate the effect of quenched surface charge disorder on electrostatic interactions between two charged surfaces in the presence of dielectric inhomogeneities and added salt. We show that in the linear weak-coupling regime (i.e., by including mean-field and Gaussian-fluctuations contributions), the image-charge effects lead to a non-zero disorder-induced interaction free energy between two surfaces of equal mean charge that can be repulsive or attractive depending on the dielectric mismatch across the bounding surfaces and the exact location of the disordered charge distribution.Comment: 7 pages, 2 figure

Electrostatic Interactions of Asymmetrically Charged Membranes

We predict the nature (attractive or repulsive) and range (exponentially screened or long-range power law) of the electrostatic interactions of oppositely charged and planar plates as a function of the salt concentration and surface charge densities (whose absolute magnitudes are not necessarily equal). An analytical expression for the crossover between attractive and repulsive pressure is obtained as a function of the salt concentration. This condition reduces to the high-salt limit of Parsegian and Gingell where the interaction is exponentially screened and to the zero salt limit of Lau and Pincus in which the important length scales are the inter-plate separation and the Gouy-Chapman length. In the regime of low salt and high surface charges we predict - for any ratio of the charges on the surfaces - that the attractive pressure is long-ranged as a function of the spacing. The attractive pressure is related to the decrease in counter-ion concentration as the inter-plate distance is decreased. Our theory predicts several scaling regimes with different scaling expressions for the pressure as function of salinity and surface charge densities. The pressure predictions can be related to surface force experiments of oppositely charged surfaces that are prepared by coating one of the mica surfaces with an oppositely charged polyelectrolyte

Correlated disordered interactions on Potts models

Using a weak-disorder scheme and real-space renormalization-group techniques, we obtain analytical results for the critical behavior of various q-state Potts models with correlated disordered exchange interactions along d1 of d spatial dimensions on hierarchical (Migdal-Kadanoff) lattices. Our results indicate qualitative differences between the cases d-d1=1 (for which we find nonphysical random fixed points, suggesting the existence of nonperturbative fixed distributions) and d-d1>1 (for which we do find acceptable perturbartive random fixed points), in agreement with previous numerical calculations by Andelman and Aharony. We also rederive a criterion for relevance of correlated disorder, which generalizes the usual Harris criterion.Comment: 8 pages, 4 figures, to be published in Physical Review

Phase behavior of a fluid with competing attractive and repulsive interactions

Fluids in which the interparticle potential has a hard core, is attractive at moderate separations, and repulsive at greater separations are known to exhibit novel phase behavior, including stable inhomogeneous phases. Here we report a joint simulation and theoretical study of such a fluid, focusing on the relationship between the liquid-vapor transition line and any new phases. The phase diagram is studied as a function of the amplitude of the attraction for a certain fixed amplitude of the long ranged repulsion. We find that the effect of the repulsion is to substitute the liquid-vapor critical point and a portion of the associated liquid-vapor transition line, by two first order transitions. One of these transitions separates the vapor from a fluid of spherical liquidlike clusters; the other separates the liquid from a fluid of spherical voids. At low temperature, the two transition lines intersect one another and a vapor-liquid transition line at a triple point. While most integral equation theories are unable to describe the new phase transitions, the Percus Yevick approximation does succeed in capturing the vapor-cluster transition, as well as aspects of the structure of the cluster fluid, in reasonable agreement with the simulation results.Comment: 15 pages, 20 figure

Kinetics of Surfactant Adsorption at Fluid/Fluid Interfaces: Non-ionic Surfactants

We present a model treating the kinetics of adsorption of soluble surface-active molecules at the interface between an aqueous solution and another fluid phase. The model accounts for both the diffusive transport inside the solution and the kinetics taking place at the interface using a free-energy formulation. In addition, it offers a general method of calculating dynamic surface tensions. Non-ionic surfactants are shown, in general, to undergo a diffusion-limited adsorption, in accord with experimental findings.Comment: 6 pages, 3 figures, see also cond-mat/960814

Attractive instability of oppositely charged membranes induced by charge density fluctuations

We predict the conditions under which two oppositely charged membranes show a dynamic, attractive instability. Two layers with unequal charges of opposite sign can repel or be stable when in close proximity. However, dynamic charge density fluctuations can induce an attractive instability and thus facilitate fusion. We predict the dominant instability modes and timescales and show how these are controlled by the relative charge and membrane viscosities. These dynamic instabilities may be the precursors of membrane fusion in systems where artificial vesicles are engulfed by biological cells of opposite charge

Effective zero-thickness model for a conductive membrane driven by an electric field

The behavior of a conductive membrane in a static (DC) electric field is investigated theoretically. An effective zero-thickness model is constructed based on a Robin-type boundary condition for the electric potential at the membrane, originally developed for electrochemical systems. Within such a framework, corrections to the elastic moduli of the membrane are obtained, which arise from charge accumulation in the Debye layers due to capacitive effects and electric currents through the membrane and can lead to an undulation instability of the membrane. The fluid flow surrounding the membrane is also calculated, which clarifies issues regarding these flows sharing many similarities with flows produced by induced charge electro-osmosis (ICEO). Non-equilibrium steady states of the membrane and of the fluid can be effectively described by this method. It is both simpler, due to the zero thickness approximation which is widely used in the literature on fluid membranes, and more general than previous approaches. The predictions of this model are compared to recent experiments on supported membranes in an electric field.Comment: 14 pages, 5 figure