Short-time rotational diffusion in monodisperse charge-stabilized colloidal suspensions

We investigate the combined effects of electrostatic interactions and hydrodynamic interactions on the short-time rotational self-diffusion coefficient in charge-stabilized suspensions. We calculate this coefficient as a function of volume fraction for various effective particle charges and amounts of added electrolyte. The influence of the hydrodynamic interactions on the rotational diffusion coefficient is less pronounced for charged particles than for uncharged ones. Salt-free suspensions are weakly influenced by hydrodynamic interactions. For these strongly correlated systems we obtain a quadratic volume fraction-dependence of the diffusion coefficient, which is well explained in terms of an effective hard sphere model.Comment: 21 pages, LaTeX, 7 Postscript figures included using epsf, to appear in Physica

Aggregation of self-propelled colloidal rods near confining walls

Non-equilibrium collective behavior of self-propelled colloidal rods in a confining channel is studied using Brownian dynamics simulations and dynamical density functional theory. We observe an aggregation process in which rods self-organize into transiently jammed clusters at the channel walls. In the early stage of the process, fast-growing hedgehog-like clusters are formed which are largely immobile. At later stages, most of these clusters dissolve and mobilize into nematized aggregates sliding past the walls.Comment: 5 pages, 4 figure

Electrokinetic and hydrodynamic properties of charged-particles systems: From small electrolyte ions to large colloids

Dynamic processes in dispersions of charged spherical particles are of importance both in fundamental science, and in technical and bio-medical applications. There exists a large variety of charged-particles systems, ranging from nanometer-sized electrolyte ions to micron-sized charge-stabilized colloids. We review recent advances in theoretical methods for the calculation of linear transport coefficients in concentrated particulate systems, with the focus on hydrodynamic interactions and electrokinetic effects. Considered transport properties are the dispersion viscosity, self- and collective diffusion coefficients, sedimentation coefficients, and electrophoretic mobilities and conductivities of ionic particle species in an external electric field. Advances by our group are also discussed, including a novel mode-coupling-theory method for conduction-diffusion and viscoelastic properties of strong electrolyte solutions. Furthermore, results are presented for dispersions of solvent-permeable particles, and particles with non-zero hydrodynamic surface slip. The concentration-dependent swelling of ionic microgels is discussed, as well as a far-reaching dynamic scaling behavior relating colloidal long- to short-time dynamics

Colloidal glass transition: Beyond mode-coupling theory

A new theory for dynamics of concentrated colloidal suspensions and the colloidal glass transition is proposed. The starting point is the memory function representation of the density correlation function. The memory function can be expressed in terms of a time-dependent pair-density correlation function. An exact, formal equation of motion for this function is derived and a factorization approximation is applied to its evolution operator. In this way a closed set of equations for the density correlation function and the memory function is obtained. The theory predicts an ergodicity breaking transition similar to that predicted by the mode-coupling theory, but at a higher density.Comment: to be published in PR

Non-monotonic density dependence of the diffusion of DNA fragments in low-salt suspensions

The high linear charge density of 20-base-pair oligomers of DNA is shown to lead to a striking non-monotonic dependence of the long-time self-diffusion on the concentration of the DNA in low-salt conditions. This generic non-monotonic behavior results from both the strong coupling between the electrostatic and solvent-mediated hydrodynamic interactions, and from the renormalization of these electrostatic interactions at large separations, and specifically from the dominance of the far-field hydrodynamic interactions caused by the strong repulsion between the DNA fragments.Comment: 4 pages, 2 figures. Physical Review E, accepted on November 24, 200

Rotational and translational self-diffusion in concentrated suspensions of permeable particles

In our recent work on concentrated suspensions of uniformly porous colloidal spheres with excluded volume interactions, a variety of short-time dynamic properties were calculated, except for the rotational self-diffusion coefficient. This missing quantity is included in the present paper. Using a precise hydrodynamic force multipole simulation method, the rotational self-diffusion coefficient is evaluated for concentrated suspensions of permeable particles. Results are presented for particle volume fractions up to 45%, and for a wide range of permeability values. From the simulation results and earlier results for the first-order virial coefficient, we find that the rotational self-diffusion coefficient of permeable spheres can be scaled to the corresponding coefficient of impermeable particles of the same size. We also show that a similar scaling applies to the translational self-diffusion coefficient considered earlier. From the scaling relations, accurate analytic approximations for the rotational and translational self-diffusion coefficients in concentrated systems are obtained, useful to the experimental analysis of permeable-particle diffusion. The simulation results for rotational diffusion of permeable particles are used to show that a generalized Stokes-Einstein-Debye relation between rotational self-diffusion coefficient and high-frequency viscosity is not satisfied.Comment: 4 figure

Enhanced structural correlations accelerate diffusion in charge-stabilized colloidal suspensions

Theoretical calculations for colloidal charge-stabilized and hard sphere suspensions show that hydrodynamic interactions yield a qualitatively different particle concentration dependence of the short-time self-diffusion coefficient. The effect, however, is numerically small and hardly accessible by conventional light scattering experiments. Applying multiple-scattering decorrelation equipment and a careful data analysis we show that the theoretical prediction for charged particles is in agreement with our experimental results from aqueous polystyrene latex suspensions.Comment: 1 ps-file (MS-Word), 14 page

Self-diffusion coefficients of charged particles: Prediction of Nonlinear volume fraction dependence

We report on calculations of the translational and rotational short-time self-diffusion coefficients $D^t_s$ and $D^r_s$ for suspensions of charge-stabilized colloidal spheres. These diffusion coefficients are affected by electrostatic forces and many-body hydrodynamic interactions (HI). Our computations account for both two-body and three-body HI. For strongly charged particles, we predict interesting nonlinear scaling relations $D^t_s\propto 1-a_t\phi^{4/3}$ and $D^r_s\propto 1-a_r\phi^2$ depending on volume fraction $\phi$, with essentially charge-independent parameters $a_t$ and $a_r$. These scaling relations are strikingly different from the corresponding results for hard spheres. Our numerical results can be explained using a model of effective hard spheres. Moreover, we perceptibly improve the known result for $D^t_s$ of hard sphere suspensions.Comment: 8 pages, LaTeX, 3 Postscript figures included using eps