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The interaction of two dipolar hard spheres near a surface and under the influence of gravity and external perpendicular magnetic fields is investigated theoretically. The full ground-state phase diagram as a function of gravity and magnetic field strengths is established. A dimer (i.e., two touching beads) can only exist when the gravity and magnetic field strengths are simultaneously not too large. Thereby, upon increasing the magnetic field strength, three dimeric states emerge: a lying state (dimer axis parallel to the substrate), an inclined state (intermediate state between the lying and standing ones) and a standing state (dimer axis normal to the substrate). It is found that the orientation angles of the dimer axis and the dipole moment in the newly discovered inclined phase are related by a strikingly simple Snell-Descartes-like law. We argue that our findings can be experimentally verified in colloidal and granular systems.

International audience; Crystallization near structured substrates is explored by extensive Brownian dynamics computer simulations of two-dimensional equimolar binary colloidal suspensions. The particles are interacting via repulsive dipole-dipole forces. The two species have different (big and small) dipole moments which are tunable by an external magnetic field. A quench is realized by a sudden drastic increase of the magnetic field which formally corresponds to a quench to zero temperature. After the quench the equilibrium state is an alternating square lattice which coincides exactly with that imposed by the external wall. The relaxation behavior following the quench is explored. The amount of local crystallites with triangular and square symmetry is monitored as a function of time for different initial temperatures. It found that the number and structure of crystallites near the walls strongly depend on the wall pattern. Even though local square structures are favored energetically and the equilibrium state is an alternating square lattice, the number of triangular crystallites close to the wall which has outermost fixed small particles is significantly higher than in the unconfined case. The actual number of triangular clusters depends on the depth of the quench. This effect is not contained in classical nucleation theory.

We studied the structures formed in aqueous dispersions of charged colloidal spheres under a constant low salt concentration of c = 6 × 10−6 mol l−1. Particles of diameter 2a = 1000 nm were confined to a low angle wedge geometry with plate separation 0

A review is given on recent studies of charged colloidal suspensions and polyelectrolytes both in static and non-equilibrium situations. As far as static equilibrium situations are concerned, we discuss three different problems: 1) Sedimentation density profiles in charged suspensions are shown to exhibit a stretched non-bariometric wing at large heights and binary suspensions under gravity can exhibit an analog of the brazil-nut effect known from granular matter, i.e. the heavier particles settle on top of the lighter ones. 2) Soft polyelectrolyte systems like polyelectrolyte stars and microgels show an ultra-soft effective interaction and this results into an unusual equilibrium phase diagram including reentrant melting transitions and stable open crystalline lattices. 3) The freezing transition in bilayers of confined charged suspensions is discussed and a reentrant behaviour is obtained. As far as nonequilibrium problems are concerned, we discuss an interface instability in oppositely driven colloidal mixtures and discuss possible approaches to simulate electrokinetic effects in charged suspensions.

In this article we review the complexation behavior of charged polymers adsorbed onto charged substrates. In the first part we summarize the results obtained on the adsorption properties of a single polyelectrolyte chain with one or several oppositely charged spherical colloids. The results of various simulational studies are compared with theoretical predictions. After that, we show that under strong electrostatic coupling conditions one can also obtain complexations, where chain and colloid carry the same charge (like-charge complexation). This effect is due to counterion correlation effects. Finally, we investigate the case of polyelectrolyte multilayers structures, which are composed of alternating polycations and polyanions on various substrate geometries. This structure, normally obtained by a so-called layer-by-lay deposition, is very stable experimentally, but only poorly understood in terms of theoretical approaches. Our simulation results suggest that short range attractive interactions (e.g., van der Waals) are important for obtaining a stable sequence of multilayers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3557–3570, 2004

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 high entropy penalty stemming from the low dimensionality of the substrate at strong curvature., 18 pages - 7 (main) EPS figs - revtex4 - to appear in J. Chem. Phys

The effects of image charges (i.e., induced surface charges of polarization) in spherical geometry and their implication for charged colloidal systems are investigated. We study analytically and exactly a single microion interacting with a dielectric sphere and discuss the similarities and discrepancies with the case of a planar interface. By means of extensive Monte Carlo (MC) simulations, we study within the framework of the primitive model the effects of image charges on the structure of the electrical double layer. Salt-free environment as well as salty solutions are considered. A remarkable finding of this study is that the position of the maximum in the counterion density (appearing at moderately surface charge density) remains quasi-identical, regardless of the counterion valence and the salt content, to that obtained within the \textit{single}-counterion system., 14 pages, 12 figures, RevTeX4, to appear in J. Chem. Phys

In this Letter we investigate the mechanism for overcharging of a single spherical colloid in the presence of aqueous salts within the framework of the primitive model by molecular dynamics (MD) simulations as well as integral-equation theory. We find that the occurrence and strength of overcharging strongly depends on the salt-ion size, and the available volume in the fluid. To understand the role of the excluded volume of the microions, we first consider an uncharged system. For a fixed bulk concentration we find that upon increasing the fluid particle size one strongly increases the local concentration nearby the colloidal surface and that the particles become laterally ordered. For a charged system the first surface layer is built up predominantly by strongly correlated counterions. We argue that this a key mechanism to produce overcharging with a low electrostatic coupling, and as a more practical consequence, to account for charge inversion with monovalent aqueous salt ions., Comment: 7 pages, 3 figs (4 EPS files). To appear in Europhysics Letters

We report the coupled effects of macroion charge discretization and counterion valence in the primitive model for spherical colloids. Instead of considering a uniformly charged surface, as it is traditionally done, we consider a more realistic situation where \textit{discrete monovalent microscopic charges} are randomly distributed over the sphere. Monovalent or multivalent counterions ensure global electroneutrality. We use molecular dynamics simulations to study these effects at the ground state and for finite temperature. The ground state analysis concerns the counterion structure and \textit{charge inversion}. Results are discussed in terms of simple analytical models. For finite temperature, strong and weak Coulomb couplings are treated. In this situation of finite temperature, we considered and discussed the phenomena of ionic pairing (pinning) and unpairing (unpinning)., 24 pages, 12 (main) figures (28 EPS files). To appear in Physica A

The effect of fixed discrete colloidal charges in the primitive model is investigated for spherical macroions. Instead of considering a central bare charge, as it is traditionally done, we distribute \textit{discrete} charges randomly on the sphere. We use molecular dynamics simulations to study this effect on various properties such as overcharging, counterion distribution and diffusion. In the vicinity of the colloid surface the electrostatic potential may considerably differ from the one obtained with a central charge. In the strong Coulomb coupling, we showed that the colloidal charge discretization qualitatively influences the counterion distribution and leads to a strong colloidal charge-counterion pair association. However, we found that \textit{charge inversion} still persists even if strong pair association is observed., 16 pages, 16 ps figures, REVTEX, accepted for publication in EPJE

In this letter, we study the ground state of two spherical macroions of identical radius, but asymmetric bare charge ((Q_{A}>Q_{B})). Electroneutrality of the system is insured by the presence of the surrounding divalent counterions. Using Molecular Dynamics simulations within the framework of the primitive model, we show that the ground state of such a system consists of an overcharged and an undercharged colloid. For a given macroion separation the stability of these ionized-like states is a function of the difference ((\sqrt{N_{A}}-\sqrt{N_{B}})) of neutralizing counterions (N_{A}) and (N_{B}). Furthermore the degree of ionization, or equivalently, the degree of overcharging, is also governed by the distance separation of the macroions. The natural analogy with ionic bonding is briefly discussed., published version

The crystalline ground state of macroions confined between two neutral parallel plates in the presence of their homogeneously spread counterions is calculated by lattice sum minimization of candidate phases involving up to six layers. For increasing macroion density, a cascade of solid-solid transitions is found involving various multilayered crystals. The cascade includes triangular monolayer and buckled bilayer as well as rhombic, squared and triangular phase structures.

The behavior of polyampholytes near a charged planar surface is studied by means of Monte Carlo simulations. The investigated polyampholytes are overall electrically neutral and made up of oppositely charged units (called blocks) that are highly charged and of the the same length. The influence of block length and substrate's surface-charge-density on the adsorption behavior is addressed. A detailed structural study, including local monomer concentration, monomer mean height, transversal chain size, interface-bond orientation correlation, is provided. It is demonstrated that adsorption is favored for long enough blocks and/or high enough Coulomb interface-ion couplings. By explicitly measuring the chain size in the bulk, it is shown that the charged interface induces either a swelling or a shrinkage of the transversal dimension of the chain depending, in a non trivial manner, on the block length., 23 pages - 10 eps figs. Submitted for publication

The behaviour of colloidal mono- and bilayers in external magnetic fields and under shear is discussed and recent progress is summarized. Superparamagnetic colloidal particles form monolayers when they are confined to a air–water interface in a hanging water droplet. An external magnetic field allows us to tune the strength of the mutual dipole–dipole interaction between the colloids and the anisotropy of the interaction can be controlled by the tilt angle of the magnetic field relative to the surface normal of the air–water interface. For sufficiently large magnetic field strength crystalline monolayers are found. The role of fluctuations in these two-dimensional crystals is discussed. Furthermore, clustering phenomena in binary mixtures of superparamagnetic particles forming fluid monolayers are predicted. Finally, we address sheared colloidal bilayers and find that the orientation of confined colloidal crystals can be tailored by a previously applied shear direction.

The behavior of highly charged short rod-like polyelectrolytes near oppositely charged planar surfaces is investigated by means of Monte Carlo simulations. A detailed microstructural study, including monomer and fluid charge distribution, and chain orientation, is provided. The influence of chain length, substrate's surface-charge-density and image forces is considered. Due to the lower chain-entropy (compared to flexible chains), our simulation data show that rod-like polyelectrolytes can, in general, better adsorb than flexible ones do. Nonetheless, at low substrate-dielectric-constant, it is found that repulsive image forces tend to significantly reduce this discrepancy., Comment: Updated results - 19 pages - 10 figs - RevTex 4

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. It is demonstrated that image forces can considerably reduce the degree of polyelectrolyte adsorption and concomitantly inhibit the charge inversion of the substrate by polyelectrolytes., 19 pages - 7 eps figs - RevTex 4 - submitted for publication

We study the counterion distribution around a spherical macroion and its osmotic pressure in the framework of the recently developed Debye-H"uckel-Hole-Cavity (DHHC) theory. This is a local density functional approach which incorporates correlations into Poisson-Boltzmann theory by adding a free energy correction based on the One Component Plasma. We compare the predictions for ion distribution and osmotic pressure obtained by the full theory and by its zero temperature limit with Monte Carlo simulations. They agree excellently for weakly developed correlations and give the correct trend for stronger ones. In all investigated cases the DHHC theory and its computationally simpler zero temperature limit yield better results than the Poisson-Boltzmann theory., Comment: 10 pages, 4 figures, 2 tables, RevTeX4-style

We report results from a molecular dynamics (MD) simulation on the conformations of a long flexible polyelectrolyte complexed to a charged sphere, \textit{both negatively charged}, in the presence of neutralizing counterions in the strong Coulomb coupling regime. The structure of this complex is very sensitive to the charge density of the polyelectrolyte. For a fully charged polyelectrolyte the polymer forms a dense two-dimensional "disk", whereas for a partially charged polyelectrolyte the monomers are spread over the colloidal surface. A mechanism involving the \textit{overcharging} of the polyelectrolyte by counterions is proposed to explain the observed conformations., Comment: 4 pages, 4 figures (6 EPS files)

We investigate spherical macroions in the strong Coulomb coupling regime within the primitive model in salt-free environment. Molecular dynamics (MD) simulations are used to elucidate the effect of $discrete$ macroion charge distribution on charge inversion. A systematic comparison is made with the charge inversion obtained in the conventional continuous charge distribution. Furthermore the effect of multivalent counterions is reported., 6 pages, LATEX (elsevier), 4 EPS files - Proceedings of CCP 2001 (Conference on Computational Physics 2001, Aachen, Germany 5-8 September 2001) - To appear in Computer Physics Communications

The adsorption of highly \textit{oppositely} charged flexible polyelectrolytes onto a charged spherical surface is investigated by means of Monte Carlo simulations in a fashion which resembles the layer-by-layer deposition technique introduced by Decher. Electroneutrality is insured at each step by the presence of monovalent counterions (anions and cations). We study in detail the structure of the \textit{equilibrium} complex. Our investigations of the first few layer formations strongly suggest that multilayering in spherical geometry is not possible as an equilibrium process with purely electrostatic interactions. We especially focus on the influence of specific (non-electrostatic) short range attractive interactions (e.g., Van der Waals) on the stability of the multilayers., Comment: 24 Pages - 15 (main) Figs - RevTeX 4 - published version

We investigate spherical macroions in the strong Coulomb coupling regime within the primitive model in salt-free environment. We first show that the ground state of an isolated colloid is naturally overcharged by simple electrostatic arguments illustrated by the Gillespie rule. We furthermore demonstrate that in the strong Coulomb coupling this mechanism leads to ionized states and thus to long range attractions between like-charged spheres. We use molecular dynamics simulations to study in detail the counterion distribution for one and two highly charged colloids for the ground state as well as for finite temperatures. We compare our results in terms of a simple version of a Wigner crystal theory and find excellent qualitative and quantitative agreement., 30 pages and 17 PS figures. REVTEX. Minor changes. To appear in Phys Rev E

We report a mechanism which can lead to long range attractions between like-charged spherical macroions, stemming from the existence of metastable ionized states. We show that the ground state of a single highly charged colloid plus a few excess counterions is overcharged. For the case of two highly charged macroions in their neutralizing divalent counterion solution we demonstrate that, in the regime of strong Coulomb coupling, the counterion clouds are very likely to be unevenly distributed, leading to one overcharged and one undercharged macroion. This long-living metastable configuration in turn leads to a long range Coulomb attraction., REVTEX-published version

The dynamics of an adsorbed polymer chain along the substrate is studied using Brownian dynamics computer simulations of a bead-spring model. The polymer is end-functionalized and exposed both to a linear shear flow and an external field oscillatory in time which couples oppositely to the end beads and acts normal to the substrate. Different propagation modes are identified including a waddling-like and somersault-like polymer motion.

Recent progress in the understanding of the effect of electrostatics in soft matter is presented. A vast amount of materials contains ions ranging from the molecular scale (e.g., electrolyte) to the meso/macroscopic one (e.g., charged colloidal particles or polyelectrolytes). Their (micro)structure and physicochemical properties are especially dictated by the famous and redoubtable long-ranged Coulomb interaction. In particular theoretical and simulational aspects, including the experimental motivations, will be discussed., Topical review

Shear-induced stretching of polymer chains adsorbed on a planar substrate is explored by atomic force microscopy experiments to visualize chain configurations of a dried spinning droplet containing poly[methacryloyloxyethyl-dimethyl-(3-pyrrol-1-yl-propyl)ammonium bromide] (PME-D-AB) in solution. For increasing shear rates, a considerable proportion of stretched chain configurations is found, which is characterized by an increasing (positive) skewness of the chain size distribution function. This behavior is also reproduced by Brownian dynamics computer simulations if the shear gradient direction is perpendicular to the wall, but not for the situation where the shear vorticity is normal to the wall.