Search

We study the structure of complexes formed between ionic surfactants (SF) and a single oppositely charged polyelectrolyte (PE) chain. For our computer simulation we use the ``primitive'' electrolyte model: while the polyelectrolyte is modeled by a tethered chain of charged hard sphere beads, the surfactant molecules consist of a single charged head bead tethered to a tail of tethered hard spheres. A hydrophobic attraction between the tail beads is introduced by assuming a Lennard-Jones potential outside the hard-sphere diameter. As a function of the strengths of both the electrostatic and the hydrophobic interactions, we find the following scenario: switching on and increasing the electrostatic forces first leads to a stretching of the PE and then by condensation of SF to the formation of a complex. For vanishing hydrophobic forces this complex has the architecture of a molecular bottle-brush cylindrically centered around the stretched PE molecule. Upon increasing the hydrophobic attraction between the SF tails, a transition occurs inverting this structure to a spherical micelle with a neutral core of SF tails and a charged corona of SF heads with the PE molecule wrapped around. At intermediate hydrophobicity there is a competition between the two structures indicated by a non-monotonic dependence of the shape as function of the Coulomb strength, favoring the cylindrical shape for weak and the spherical micellar complex for strong interaction., Comment: 11 pages, 12 figures

Recently it has been shown that a strongly interacting colloidal mixture consisting of oppositely driven particles, undergoes a nonequilibrium transition towards lane formation provided the driving strength exceeds a threshold value. We predict here a reentrance effect in lane formation: for fixed high driving force and increasing particle densities, there is first a transition towards lane formation which is followed by another transition back to a state with no lanes. Our result is obtained both by Brownian dynamics computer simulations and by a phenomenological dynamical density functional theory., Comment: 4 pages, 2 figures

By employing computer simulations for a model binary mixture, we show that a reentrant glass transition upon adding a second component only occurs if the ratio $\alpha$ of the short-time mobilities between the glass-forming component and the additive is sufficiently small. For $\alpha \approx 1$, there is no reentrant glass, even if the size asymmetry between the two components is large, in accordance with two-component mode coupling theory. For $\alpha \ll 1$, on the other hand, the reentrant glass is observed and reproduced only by an effective one-component mode coupling theory., Comment: 4 pages, 3 figures

The concept of effective depletion forces between two fixed big colloidal particles in a bath of small particles is generalized to a non-equilibrium situation where the bath of small Brownian particles is flowing around the big particles with a prescribed velocity. In striking contrast to the equilibrium case, the non-equilibrium forces violate Newton's third law, are non-conservative and strongly anisotropic, featuring both strong attractive and repulsive domains., Comment: 4 pages, 3 figures

Computer simulations and theory are used to systematically investigate how the effective force between two big colloidal spheres in a sea of small spheres depends on the basic (big-small and small-small) interactions. The latter are modeled as hard-core pair potentials with a Yukawa tail which can be both repulsive or attractive. For a repulsive small-small interaction, the effective force follows the trends as predicted by a mapping onto an effective non-additive hard-core mixture: both a depletion attraction and an accumulation repulsion caused by small spheres adsorbing onto the big ones can be obtained depending on the sign of the big-small interaction. For repulsive big-small interactions, the effect of adding a small-small attraction also follows the trends predicted by the mapping. But a more subtle ``repulsion through attraction'' effect arises when both big-small and small-small attractions occur: upon increasing the strength of the small-small interaction, the effective potential becomes more repulsive. We have further tested several theoretical methods against our computer simulations: The superposition approximation works best for an added big-small repulsion, and breaks down for a strong big-small attraction, while density functional theory is very accurate for any big-small interaction when the small particles are pure hard-spheres. The theoretical methods perform most poorly for small-small attractions., Comment: submitted to PRE; New version includes an important quantitative correction to several of the simulations. The main conclusions remain unchanged though

We examine sedimentation density profiles of star polymer solutions as an example of colloidal systems in sedimentation equilibrium which exhibit reentrant melting in their bulk phase diagram. Phase transitions between a fluid and a fluid with an intercalated solid are observed below a critical gravitational strength $\alpha^{*}$. Characteristics of the two fluid-solid interfaces in the density profiles occurring in Monte Carlo simulations for $\alpha < \alpha^{*}$ are in agreement with scaling laws put forth in the framework of a phenomenological theory. Furthermore we detect density oscillations at the fluid-gas interface at high altitudes for high gravitational fields, which are verified with density functional theory and should be observable in surface scattering experiments., Comment: 10 pages, 6 figures

We examine the demixing transition in star polymer-colloid mixtures for star arm numbers f=2,6,16,32 and different star-colloid size ratios. Theoretically, we solve the thermodynamically self-consistent Rogers-Young integral equations for binary mixtures using three effective pair potentials obtained from direct molecular computer simulations. The numerical results show a spinodal instability. The demixing binodals are approximately calculated, and found to be consistent with experimental observations., Comment: 4 pages, 4 figures, submitted to PRL

We study the structural and thermodynamic properties of a model of point particles interacting by means of a Gaussian pair potential first introduced by Stillinger [Stillinger F H 1976 J. Chem. Phys. 65, 3968]. By employing integral equation theories for the fluid state and comparing with Monte Carlo simulation results, we establish the limits of applicability of various common closures and examine the dependence of the correlation functions of the liquid on the density and temperature. We employ a simple, mean-field theory for the high density domain of the liquid and demonstrate that at infinite density the mean-field theory is exact and that the system reduces to an `infinite density ideal gas', where all correlations vanish and where the hypernetted chain (HNC) closure becomes exact. By employing an Einstein model for the solid phases, we subsequently calculate quantitatively the phase diagram of the model and find that the system possesses two solid phases, face centered cubic and body centered cubic, and also displays reentrant melting into a liquid at high densities. Moreover, the system remains fluid at all densities when the temperature exceeds 1% of the strength of the interactions., Comment: 22 pages, 10 figures

We examine in full generality the phase behavior of systems whose constituent particles interact by means of potentials which do not diverge at the origin, are free of attractive parts and decay fast enough to zero as the interparticle separation r goes to infinity. By employing a mean field-density functional theory which is shown to become exact at high temperatures and/or densities, we establish a criterion which determines whether a given system will freeze at all temperatures or it will display reentrant melting and an upper freezing temperature., Comment: 5 pages, 3 figures, submitted to PRL on March 29, 2000 New version: 10 pages, 9 figures, forwarded to PRE on October 16, 2000

The present review summarizes and assesses recent theoretical and experimental advances, with special emphasis on the effective interaction between charge-stabilized colloids, in the bulk or in confined geometries, and on the ambiguities of defining an effective charge of the colloidal particles. Some consideration is given to the often neglected discrete solvent effects., Comment: 27 pages, 5 figures. This is an unedited draft of an article which has been submitted for the Annual Review of Physical Chemistry, Volume 51, 2000, bye Annual Reviews http://AnnualReviews.org

Freezing of charge-stabilized colloidal suspensions and relative stabilities of crystals and quasicrystals are studied using thermodynamic perturbation theory. Macroion interactions are modelled by effective pair potentials combining electrostatic repulsion with polymer-depletion or van der Waals attraction. Comparing free energies -- counterion terms included -- for elementary crystals and rational approximants to icosahedral quasicrystals, parameters are identified for which one-component quasicrystals are stabilized by a compromise between packing entropy and cohesive energy., Comment: 6 pages, 4 figures