Computer Simulations of charged systems

The electrophoretic behaviour of flexible polyelectrolyte chains ranging from single monomers up to long fragments of hundred repeat units is studied by a mesoscopic simulation approach. Abstracting from the atomistic details of the polyelectrolyte and the fluid, a coarse-grained molecular dynamics model connected to a mesoscopic fluid described by the Lattice Boltzmann approach is used to investigate free-solution electrophoresis. Our study demonstrates the importance of hyd...

The adsorption of highly \textit{oppositely} charged flexible polyelectrolytes (PEs) on a charged planar substrate is investigated by means of Monte Carlo (MC) simulations. We study in detail the equilibrium structure of the first few PE layers. The influence of the chain length and of a (extra) non-electrostatic short range attraction between the polycations and the negatively charged substrate is considered. We show that the stability as well as the microstructure of the PE...

Colloidal suspensions and polyelectrolyte solutions containing multivalent counterions can exhibit some very counter-intuitive behavior usually associated with the low temperature physics. There are two particularly striking phenomena resulting from strong electrostatic correlations. One is the like-charge attraction and the second is the polyion overcharging. In this contribution we will concentrate on the problem of overcharging. In particular we will explore the kinetic li...

The ion distribution around charged colloids in solution has been investigated intensely during the last decade. However, few theoretical approaches have included the influence of variation in the dielectric permittivity within the system, let alone in the surrounding solvent. In this article, we introduce two relatively new methods that can solve the Poisson equation for systems with varying permittivity. The harmonic interpolation method (HIM) approximately solves the Green...

We develop a computational method for modeling electrostatic interactions of arbitrarily-shaped, polarizable objects on colloidal length scales, including colloids/nanoparticles, polymers, and surfactants, dispersed in explicit ion electrolytes and nonionic solvents. Our method computes the nonuniform polarization charge distribution induced in a colloidal particle by both externally applied electric fields and local electric fields arising from other charged objects in the d...

The adsorption of highly charged flexible polycations and polyanions on a charged cylindrical substrate is investigated by means of Monte Carlo (MC) simulations. A detailed structural study, including monomer and fluid charge distributions, is provided. The influence of a short range attraction between the polycations and the negatively charged substrate is also considered. We demonstrate that the building up of multilayer structures is highly prohibited mainly due to the hig...

The influence of the chain degree of ionization on the adsorption of weak polyelectrolytes on neutral and on oppositely and likely charged surfaces is investigated for the first time, by means of Monte Carlo simulations with the mesoscopic interaction model known as dissipative particle dynamics. The electrostatic interactions are calculated using the three-dimensional Ewald sum method, with an appropriate modification for confined systems. Effective wall forces confine the l...

The adsorption of flexible and highly charged polyelectrolytes onto oppositely charged planar surfaces is investigated by means of Monte Carlo simulations. The effect of image forces stemming from the dielectric discontinuity at the substrate interface is considered. The influence, at fixed polyelectrolyte volume fraction, of chain length and surface-charge density is also considered. A detailed structural study, including monomer and fluid charge distributions, is provided. ...

We report on a study of the shape of a stiff, charged rod that is subjected to equal and opposite force couples at its two ends. Unlike a neutral elastic rod, which forms a constant curvature configuration under such influences, the charged rod tends to flatten in the interior and accumulate the curvature in the end points, to maximally reduce the electrostatic self-repulsion. The effect of this nonuniform bending on the effective elasticity and on the statistical conformatio...

Ion distributions in dilute polyelectrolyte solutions are studied by means of Langevin dynamics simulations. We show that the distributions depend on the conformation of a chain while the conformation is determined by the chain stiffness and the salt concentration. We observe that the monovalent counterions originally condensed on a chain can be replaced by the multivalent ones dissociated from the added salt due to strong electrostatic interaction. These newly condensed ions...