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The Wulff construction for the equilibrium shape of a crystal, being in coexistence with its vapor, is applied to a situation very near the triple point where the liquid phase becomes thermodynamically stable, too. This is particularly interesting if some planes of the crystal melt and other ones do not. In this case, it is found that the equilibrium shape exhibits liquid lenses on the crystal which match with a finite angle to the crystalline part. The results are compared with recent equilibrium shape measurements of lead crystallites.

We study an exactly soluble model for planar interfacial kinetics for both locally conserved and nonconserved order parameters, where the Landau–Ginzburg potential is approximated by two parabolas. Long‐range interactions with arbitrary interaction kernels are included. In particular, the relaxation of the initial order parameter interfacial profile to its equilibrium profile is considered. Furthermore, the steady‐state solution of planar interfacial growth for a nonconserved order parameter is determined. Here, the influence of a second nonconserved order parameter is also discussed.

We describe a van der Waals approach with multiple order parameter for surface melting near the triple pointTT which is based on density functional theory for bulk freezing. The occurrence of surface-induced melting, non-melting or blocked (incomplete) melting is governed by the specific form of the long-ranged tail in the interparticle potential. In the case of melting, the residual crystallinity at the vapor side of the quasi-liquid layer is shown to decay with a stretched exponential (power) law inTT-T for long-(short-) ranged interparticle forces

Thermostatistical properties of hard sphere and hard disk systems are discussed. In particular we focus on phase transitions such as freezing in the thermodynamic limit. Results based on theory and computer simulations are given. It is emphasized that suspensions of sterically-stabilized colloids represent excellent realizations of the hard sphere model. Finally a survey of current research activities for hard sphere systems is presented and some recent results are summarized.

A cell theory is proposed to obtain the full phase diagram of hard spherocylinders involving isotropic, nematic, smectic as well as plastic and aligned crystalline phases. Despite its conceptual and numerical simplicity this free-volume theory yields the correct topology of the phase diagram in semi-quantitative agreement with recent computer simulations.

Applying a density-functional-based perturbation theory, we examine the phase behaviour of model colloidal systems characterized by hard core and additional piecewise-constant repulsive or attractive interactions. For sufficiently narrow square-shoulder repulsions, the theory predicts coexistence between expanded and condensed isostruc tural (f.c.c.) crystals, in quantitative agreement with available simulation data. A square-well attraction of equal width results in a solid-solid critical point at lower density and higher temperature and a significantly wider coexistence region. Adding a constant long-ranged attraction leads to a novel phase diagram exhibiting a quadruple point, where two fluid phases and two solid phases coexist simultaneously.

The freezing transition of hard sphere colloids confined between two parallel hard plates is studied for different plate distances ranging from one to two particle diameters. Using Monte Carlo simulations and free volume theory, the full phase diagram is obtained exhibiting solid-to-solid transitions between buckled, rhombic and layered crystals involving several triangular or square layers. While the fluid freezing transition is always strongly first order, both strong and extremely weak transitions occur between different crystalline structures. These predictions should be experimentally observable in confined suspensions of sterically stabilized or highly salted charge-stabilized colloidal particles.

Using computer simulations of the primitive model, we calculate the effective force acting onto a single macroion and onto a macroion pair in the presence of slitlike confinement between charged plates. For moderate Coulomb coupling, we find that this force is repulsive. Under strong coupling conditions, however, the sign of the force depends on the distance to the plates and on the interparticle distance. In particular, the particle-plate interaction becomes strongly attractive for small distances, which leads to colloidal crystalline layers near the plates as observed in recent experiments.

In dense solution high functionality star polymers show ordering phenomena which give rise to a well-pronounced peak in the static structure factor, S exp(Q), observed by small-angle neutron scattering. The concentration dependence of S exp (Q) gives evidence for unusual phase behaviour as predicted by theory. In addition, the dynamics of the star polymer solutions is dominated by an increasing amount of structural arrest with increasing concentration. The mean square displacement obtained from neutron spin-echo spectroscopy is compared to the blob size obtained from dynamic light scattering. Thermal energy enables each star core to perform restricted motion over a spatial extent equal to the blob size of the surrounding dense star polymer solution.

Using extensive Brownian dynamics computer simulations, the long-time self-diffusion coefficient is calculated for Gaussian-core particles as a function of the number density. Both spherical and rod-like particles interacting via Gaussian segments ar$ For increasing concentration we find that the translational self-diffusion behaves non-monotonically reflecting the structural reentrance effect in the equilibrium phase diagram. Both in the limits of zero and infinite concentration, it approaches its short-time value. The microscopic Medina-Noyola theory qualitatively accounts for the translational long-time diffusion. The long-time orientational diffusion coefficient for Gaussian rods, on the other hand, remains very close to its short-time counterpart for any density. Some implications of the weak translation-rotation coupling for ultrasoft rods are discussed., Comment: 5 pages, 5 figures

The influence of hydrodynamic interactions on lane formation of oppositely charged driven colloidal suspensions is investigated using Brownian dynamics computer simulations performed on the Rotne-Prager level of the mobility tensor. Two cases are considered, namely sedimentation and electrophoresis. In the latter case the Oseen contribution to the mobility tensor is screened due to the opposite motion of counterions. The simulation results are compared to that resulting from simple Brownian dynamics where hydrodynamic interactions are neglected. For sedimentation, we find that hydrodynamic interactions strongly disfavor laning. In the steady-state of lanes, a macroscopic phase separation of lanes is observed. This is in marked contrast to the simple Brownian case where a finite size of lanes was obtained in the steady-state. For strong Coulomb interactions between the colloidal particles a lateral square lattice of oppositely driven lanes is stable similar to the simple Brownian dynamics. In an electric field, on the other hand, the behavior is found in qualitative and quantitative accordance with the case of neglected hydrodynamics., Comment: 6 figures

We examine the rheological transition from an arrested to a fluid state for different mixtures of star polymers with varying functionality and size ratios. As a general trend, we find that addition of smaller star polymers in an arrested, concentrated solution of larger ones brings about melting of the large star glass. At the same time, the dependence of the amount of additives needed to melt the glass has a nontrivial dependence on the size ratio. Theoretical analysis, based on effective interactions and Mode Coupling Theory, reproduces the experimental results and helps identify two distinct types of glasses in the composite system.

The phase diagram of binary mixtures of particles interacting via a pair potential of parallel dipoles is computed at zero temperature as a function of composition and the ratio of their magnetic susceptibilities. Using lattice sums, a rich variety of different stable crystalline structures is identified including $A_mB_n$ structures. [$A$ $(B)$ particles correspond to large (small) dipolar moments.] Their elementary cells consist of triangular, square, rectangular or rhombic lattices of the $A$ particles with a basis comprising various structures of $A$ and $B$ particles. For small (dipolar) asymmetry there are intermediate $AB_2$ and $A_2B$ crystals besides the pure $A$ and $B$ triangular crystals. These structures are detectable in experiments on granular and colloidal matter., Comment: 6 pages - 2 figs - phase diagram updated

We provide a theoretical analysis for the intermediate scattering function typically measured in depolarized dynamic light scattering experiments. We calculate the field autocorrelation function $g_1^{\rm VH}(Q,t)$ in dependence on the wave vector $Q$ and the time $t$ explicitly in a vertical-horizontal scattering geometry for differently shaped solids of revolution. The shape of prolate cylinders, spherocylinders, spindles, and double cones with variable aspect ratio is expanded in rotational invariants $f_{lm}(r)$. By Fourier transform of these expansion coefficients, a formal multipole expansion of the scattering function is obtained, which is used to calculate the weighting coefficients appearing in the depolarized scattering function. In addition to translational and rotational diffusion, especially the translational-rotational coupling of shape-anisotropic objects is considered. From the short-time behavior of the intermediate scattering function, the first cumulants $\Gamma(Q)$ are calculated. In a depolarized scattering experiment, they deviate from the simple proportionality to $Q^2$. The coefficients $f_{lm}(Q)$ strongly depend on the geometry and aspect ratio of the particles. The time dependence, in addition, is governed by the translational and rotational diffusion tensors, which are calculated by means of bead models for differently shaped particles in dependence on their aspect ratio. Therefore, our analysis shows how details of the particle shape---beyond their aspect ratio---can be determined by a precise scattering experiment. This is of high relevance in understanding smart materials which involve suspensions of anisotropic colloidal particles., Comment: 24 pages, 13 figures

The self-propulsion of artificial and biological microswimmers (i.e., active colloidal particles) has often been modelled by using a force and a torque entering into the overdamped equations for the Brownian motion of passive particles. This seemingly contradicts the fact that a swimmer is force-free and torque-free, i.e., that the net force and torque on the particle vanish. Using different models for mechanical and diffusiophoretic self-propulsion, we demonstrate here that the equations of motion of microswimmers can be mapped onto those of passive particles with the shape-dependent grand resistance matrix and formally external effective forces and torques. This is consistent with experimental findings on the circular motion of artificial asymmetric microswimmers driven by self-diffusiophoresis. The concept of effective self-propulsion forces and torques significantly facilitates the understanding of the swimming paths, e.g., for a microswimmer under gravity. However, this concept has its limitations when the self-propulsion mechanism of a swimmer is disturbed either by another particle in its close vicinity or by interactions with obstacles, such as a wall., Comment: 19 pages, 2 figures

We study the response of a nematic colloidal dispersion of rods to a driven probe particle which is dragged with high speed through the dispersion perpendicular to the nematic director. In front of the dragged particle, clusters of rods are generated which rhythmically grow and dissolve by rotational motion. We find evidence for a mesoscopic cluster-cluster correlation length, {\em independent} of the imposed drag speed. Our results are based on non-equilibrium Brownian dynamics computer simulations and in line with a dynamical scaling theory., Comment: 4 pages, 5 figures, to appear in Phys. Rev. Lett

A density functional theory of two-dimensional freezing is presented for a soft interaction potential that scales as inverse cube of particle distance. This repulsive potential between parallel, induced dipoles is realized for paramagnetic colloids on an interface, which are additionally exposed to an external magnetic field. An extended modified weighted density approximation which includes correct triplet correlations in the liquid state is used. The theoretical prediction of the freezing transition is in good agreement with experimental and simulation data., Comment: 7 pages, 3 figures, submitted 2006

We study the dynamics of soft colloids interacting via a Gaussian pair potential in an external moving potential which is periodic in the spatial coordinate of the direction of motion. Both dynamical density functional theory and Brownian dynamics computer simulations are used to predict the steady-state density profiles. Two different situations are investigated: the first corresponds to a light wave that travels with a constant velocity v through the quiescent solvent containing the colloidal suspension. The second setup consists of two parallel repulsive walls with a periodic topographical substructure. One of the walls is at rest relative to the solvent while the other is in motion, inducing a shearing of the suspension. In the first case, we find that the amplitude of the steady-state density behaves nonmonotonically with the traveling speed v of the wave if the shape of the wave contains an edge: for increasing v , it first grows and then decreases. In the second setup we show that a strongly confined suspension induces a shear resistance which is a nonmonotonic function of the wall velocity. These effects are verifiable in real-space experiments on colloidal suspensions exposed to external laser-optical fields. In both situations, the dynamical density functional theory is in good agreement with the Brownian dynamics simulation data.

We examine the vitrification and melting of asymmetric star polymers mixtures by combining rheological measurements with mode coupling theory. We identify two types of glassy states, a {\it single} glass, in which the small component is fluid in the glassy matrix of the big one and a {\it double} glass, in which both components are vitrified. Addition of small star polymers leads to melting of {\it both} glasses and the melting curve has a non-monotonic dependence on the star-star size ratio. The phenomenon opens new ways for externally steering the rheological behavior of soft matter systems., 4 pages, 4 figures, accepted in Phys. Rev. Lett

Crystalline bilayers of charged colloidal suspensions which are confined between two parallel plates and sheared via a relative motion of the two plates are studied by extensive Brownian dynamics computer simulations. The charge-stabilized suspension is modeled by a Yukawa pair potential. The unsheared equilibrium configuration is two crystalline layers with a nested quadratic in-plane structure. For increasing shear rates (.)gamma, we find the following steady states: First, up to a threshold of the shear rate, there is a static solid which is elastically sheared. Above the threshold, there are two crystalline layers sliding on top of each other with a registration procedure. Higher shear rates melt the crystalline bilayers and even higher shear rates lead to a reentrant solid stratified in the shear direction. This qualitative scenario is similar to that found in previous bulk simulations. We have then studied the relaxation of the sheared steady state back to equilibrium after an instantaneous cessation of shear and found a nonmonotonic behavior of the typical relaxation time as a function of the shear rate (.)gamma. In particular, application of high shear rates accelerates the relaxation back to equilibrium since shear-ordering facilitates the growth of the equilibrium crystal. This mechanism can be used to grow defect-free colloidal crystals from strongly sheared suspensions. Our theoretical predictions can be verified in real-space experiments of strongly confined charged suspensions.

We present a theoretical analysis of the structural properties and phase behavior of spherical, loosely cross-linked ionic microgels that possess a low monomer concentration. The analysis is based on the recently derived effective interaction potential between such particles fA. R. Denton, Phys. Rev. E 67, 011804 s2003dg. By employing standard tools from the theory of the liquid state, we quantitatively analyze the pair correlations in the fluid and find anomalous behavior above the overlap concentration, similar to the cases of star-branched neutral and charged polymers. We also employ an evolutionary algorithm in order to predict the crystalline phases of the system without any a priori assumptions regarding their symmetry class. A very rich phase diagram is obtained, featuring two reentrant melting transitions and a number of unusual crystal structures. At high densities, both the Hansen‐Verlet freezing criterion fJ.-P. Hansen and L. Verlet, Phys. Rev. 184, 151 s1969dg and the Lindemann melting criterion fF. A. Lindemann, Phys. Z. 11, 609 s1910dg lose their validity. The topology of the phase diagram is altered when the steric interactions between the polymer segments become strong enough, in which case the lower-density reentrant melting disappears and the region of stability of the fluid is split into two disconnected domains, separated by intervening fcc and bcc regions. © 2005 American Institute of Physics . fDOI: 10.1063/1.1850451g

The influence of interface porosity on the wetting properties of colloid-polymer mixtures is studied within density functional theory for the Asakura-Oosawa-Vrij model at the surface of a quenched hard-sphere matrix. While the porosity hardly changes the location of the transition from partial to complete wetting at colloidal bulk gas-liquid coexistence, the onset of wetting, as signaled by the first discontinuous layering transition, can be efficiently controlled by tailoring the porosity. We furthermore find that the penetrability of the porous interface induces complete drying into the matrix upon approaching capillary coexistence.

Superparamagnetic colloidal particles confined to a flat horizontal air-water interface in an external magnetic field, which is tilted relative to the interface, form anisotropic two-dimensional crystals resulting from their mutual dipole-dipole interactions. Using real-space experiments and harmonic lattice theory we explore the mean-square displacements of the particles in the directions parallel and perpendicular to the in-plane component of the external magnetic field as a function of the tilt angle. We find that the anisotropy of the mean-square displacement behaves nonmonotonically as a function of the tilt angle and does not correlate with the structural anisotropy of the crystal.

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 effective DNA-DNA interaction force is calculated by computer simulations with explicit tetravalent counterions and monovalent salt. For overcharged DNA molecules, the interaction force shows a double-minimum structure. The positions and depths of these minima are regulated by the counterion density in the bulk. Using two-dimensional lattice sum and free energy perturbation theories, the coexisting phases for DNA bundles are calculated. A DNA-condensation and redissolution transition and a stable mesocrystal with an intermediate lattice constant for high counterion concentration are obtained., 26 pages, 10 figures

Using the recently developed effective interaction potentials between polyelectrolyte stars, we examine the structure and phase behavior of solutions of the same. The effective interaction is ultrasoft and density dependent, owing to the integration of the counterionic degrees of freedom. The latter contribute extensive volume terms that must be taken into account in drawing the phase diagram of the system. The structural behavior of the uniform fluid is characterized by anomalous structure factors, akin to those found previously for solutions of uncharged star polymers. The phase diagram of the system is very rich, featuring a fluid phase at low arm numbers of the stars, two reentrant melting regions, as well as a variety of crystal structures with unusual symmetry. The physical origin of these features can be traced back to the ultrasoft nature of the effective interaction potential.

We study the effect of shear flow on homogeneous crystal nucleation, using Brownian Dynamics simulations in combination with an umbrella sampling like technique. The symmetry breaking due to shear results in anisotropic radial distribution functions. The homogeneous shear rate suppresses crystal nucleation and leads to an increase of the size of the critical nucleus. These observations can be described by a simple, phenomenological extension of classical nucleation theory. In addition, we find that nuclei have a preferential orientation with respect to the direction of shear. On average the longest dimension of a nucleus is along the vorticity direction, while the shortest dimension is preferably perpendicular to that and slightly tilted with respect to the gradient direction., 10 pages, 8 figures, Submitted to J. Phys.: Condens. Matter

We use Brownian Dynamics simulations in combination with the umbrella sampling technique to study the effect of shear flow on homogeneous crystal nucleation. We find that a homogeneous shear rate leads to a significant suppression of the crystal nucleation rate and to an increase of the size of the critical nucleus. A simple, phenomenological extension of classical nucleation theory accounts for these observations. The orientation of the crystal nucleus is tilted with respect to the shear direction., 4 pages, 3 figures, Submitted to Phys. Rev. Lett

We apply extensive Molecular Dynamics simulations and analytical considerations in order to study the conformations and the effective interactions between weakly charged, flexible polyelectrolyte chains in salt-free conditions. We focus on charging fractions lying below 20%, for which case there is no Manning condensation of counterions and the latter can be thus partitioned in two states: those that are trapped within the region of the flexible chain and the ones that are free in the solution. We examine the partition of counterions in these two states, the chain sizes and the monomer distributions for various chain lengths, finding that the monomer density follows a Gaussian shape. We calculate the effective interaction between the centers of mass of two interacting chains, under the assumption that the chains can be modeled as two overlapping Gaussian charge profiles. The analytical calculations are compared with measurements from Molecular Dynamics simulations. Good quantitative agreement is found for charging fractions below 10%, where the chains assume coil-like configurations, whereas deviations develop for charge fraction of 20%, in which case a conformational transition of the chain towards a rodlike configuration starts to take place., 38 pages, 12 figures, 2 tables. Revised version of the manuscript. Selected for publication in the V\irtual Journal of Biological Physics Research, issue of 1 september, 2004

A DNA-protein complex modelled by a semiflexible chain and an attractive spherical core is studied in the situation when an external stretching force is acting on one end monomer of the chain while the other end monomer is kept fixed in space. Without stretching force, the chain is wrapped around the core. By applying an external stretching force, unwrapping of the complex is induced. We study the statics and the dynamics of the unwrapping process by computer simulation and simple phenomenological theory. We find two different scenarios depending on the chain stiffness: For a flexible chain, the extension of the complex scales linearly with the external force applied. The sphere-chain complex is disordered, i.e. there is no clear winding of the chain around the sphere. For a stiff chain, on the other hand, the complex structure is ordered, which is reminiscent to nucleosome. There is a clear winding number and the unwrapping process under external stretching is discontinuous with jumps of the distance-force curve. This is associated to discrete unwinding processes of the complex. Our predictions are of relevance for experiments, which measure force-extension curves of DNA-protein complexes, such as nucleosome, using optical tweezers., 8 pages, 7 figures

Colloidal suspensions have been proven to play a pivotal role of model systems in order to understand the principles of equilibrium phase transitions such as freezing and fluid‐fluid demixing. One of the main reasons for that is that real‐space studies are possible thanks to the mesoscopic length scale of the particle size. The same model character of colloidal suspensions holds in non‐equilibrium situations as e.g. represented by an external driving field (such as shear, gravity, an electric and/or magnetic field). In this paper some current examples of non‐equilibrium transitions are reviewed where recent progress has been made by theory and computer simulation. In particular, we discuss the competition between phase separation and lane formation in driven colloidal mixtures, crystal nucleation in charged suspensions under shear and chain formation of two‐dimensional superparamagnetic suspensions induced by an external magnetic field.

We employ effective interaction potentials to study the equilibrium structure and phase behavior of highly asymmetric mixtures of star polymers. We consider in particular the influence of the addition of a component with a small number of arms and a small size on a concentrated solution of large stars with a high functionality. By employing liquid integral equation theories we examine the evolution of the correlation functions of the big stars upon addition of the small ones, finding a loss of structure that can be attributed to a weakening of the repulsions between the large stars due to the presence of the small ones. We analyze this phenomenon be means of a generalized depletion mechanism which is supported by computer simulations. By applying thermodynamic perturbation theory we draw the phase diagram of the asymmetric mixture, finding that the addition of small stars melts the crystal formed by the big ones. A systematic comparison between the two- and effective one-component descriptions of the mixture that corroborates the reliability of the generalized depletion picture is also carried out., Comment: 26 pages, 9 figures, submitted to Phys. Rev. E

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

We reply to the preceding comment by Rascon and co-workers (J. Phys. Condens. Matter, vol.7, p.8211, 1995), which discusses isostructural FCC-FCC transitions in systems with short-range attractions.

The stability of different crystal lattices of two-dimensional superparamagnetic suspensions that are confined to a planar liquid-gas interface and exposed to a tilted external magnetic field is studied theoretically by lattice sum minimizations. The magnetic field induces magnetic dipoles onto the colloidal particles along its direction, whose strength can be controlled by the amplitude of the external field. The mutual interaction between the colloids is governed by dipole-dipole forces and a short-ranged repulsion having its physical origin at the presence of the colloidal cores. If the direction of the magnetic field is perpendicular to the liquid-gas interface, there is a purely repulsive interaction leading to stable triangular crystals. By tilting the external field, the interaction becomes anisotropic and a mutual attraction appears upon a threshold tilt angle. We have calculated the full phase diagram at zero temperature varying the tilt angle, the colloidal density, and the strength of the magnetic field. Apart from the triangular lattice we find a variety of stable crystal lattices including rectangular, oblique, chainlike oblique, and rhombic structures. We also present the accurate derivation of the Hamiltonian of two polarizable particles of finite arbitrary geometries in external magnetic and electric fields.

We employ effective interaction potentials between spherical polyelectrolyte microgels in order to investigate theoretically the structure, thermodynamics, and phase behavior of ionic microgel solutions. Combining a genetic algorithm with accurate free energy calculations we are able to perform an unrestricted search of candidate crystal structures. Hexagonal, body-centered orthogonal, and trigonal crystals are found to be stable at high concentrations and charges of the microgels, accompanied by reentrant melting behavior and fluid-fcc-bcc transitions below the overlap concentration.

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., 4 pages, 3 figures

We consider the Asakura-Oosawa model of hard sphere colloids and ideal polymers in contact with a porous matrix modeled by immobilized configurations of hard spheres. For this ternary mixture a fundamental measure density functional theory is employed, where the matrix particles are quenched and the colloids and polymers are annealed, i.e. allowed to equilibrate. We study capillary condensation of the mixture in a tiny sample of matrix as well as demixing and the fluid-fluid interface inside a bulk matrix. Density profiles normal to the interface and surface tensions are calculated and compared to the case without matrix. Two kinds of matrices are considered: (i) colloid-sized matrix particles at low packing fractions and (ii) large matrix particles at high packing fractions. These two cases show fundamentally different behavior and should both be experimentally realizable. Furthermore, we argue that capillary condensation of a colloidal suspension could be experimentally accessible. We find that in case (ii), even at high packing fractions, the main effect of the matrix is to exclude volume and, to high accuracy, the results can be mapped onto those of the same system without matrix via a simple rescaling., Comment: 12 pages, 9 figures, submitted to PRE

The phase diagram of crystalline bilayers of particles interacting via a Yukawa potential is calculated for arbitrary screening lengths and particle densities. Staggered rectangular, square, rhombic and triangular structures are found to be stable including a first-order transition between two different rhombic structures. For varied screening length at fixed density, one of these rhombic phases exhibits both a single and even a double reentrant transition. Our predictions can be verified experimentally in strongly confined charged colloidal suspensions or dusty plasma bilayers., Comment: 4 pages, 3 eps figs - revtex4. PRL - in press

An ab initio approach to simulate the interactions and correlations of charged rodlike colloidal particles is proposed, which combines molecular dynamics for the mesoscopic rods and classical density-functional theory for the microscopic counterions. Many-body inter-rod interactions induced by non-linear counterion screening are systematically included in this approach. It is found that these forces can satisfactorily be described by an effective Yukawa-segment model which, however, differs in general from the traditional Derjaguin-Landau-Verwey-Overbeek theory.

Combining elasticity theory with electrostatics, we calculate the actuation response of a charged multilayer film, which is composed of consecutively stacked piezoelectric and polymeric elastomer layers, with respect to an applied voltage. Depending on the individual material properties and polarity of the applied voltage, we show that the composite multilayer can exhibit actuation properties which are considerably better than the response of the individual constituents. It is also shown that there is a window for applied voltages within which the thickness of the composite film expands, a condition that cannot be achieved in single layer films. In particular, we apply and evaluate our theory for various piezoelectric and dielectric elastomers. The results obtained will be helpful to develop tailored composite materials with specific actuation characteristics.

We discuss recent developments and present new findings in the colloidal description of soft polymeric macromolecular aggregates. For various macromolecular architectures, such as linear chains, star polymers, dendrimers and polyelectrolyte stars, the effective interactions between suitably chosen coordinates are shown to be ultrasoft, i.e., they either remain finite or diverge very slowly at zero separation. As a consequence, the fluid phases have unusual characteristics, including anomalous pair correlations and mean-field like thermodynamic behaviour. The solid phases can exhibit exotic, strongly anisotropic as well as open crystal structures. For example, the diamond and the A15-phase are shown to be stable at sufficiently high concentrations. Reentrant melting and clustering transitions are additional features displayed by such systems, resulting in phase diagrams with a very rich topology. We emphasise that many of these effects are fundamentally different from the usual archetypal hard sphere paradigm. Instead, we propose that these fluids fall into the class of mean-field fluids., 22 pages, uses iopart.cls and iopart10.clo; submitted to Journal of Physics Condensed Matter, special issue in honour of professor Peter Pusey

Institut fu ¨r Theoretische Physik II, Heinrich-Heine-UniversitatDusseldorf, Universita¨tsstrase 1, D-40225 Du¨sseldorf, Germany~Received 27 November 2001; published 26 March 2002!The equilibrium structure of decoration lattices composed of colloidal particles adsorbed on periodic stripe-patterned substrates is calculated as a function of the stripe width and separation and for different interparticleinteractions. Due to a competition of length scales, a wealth of different stable decoration lattices occurs suchas triangular, quadratic, rhombic, kitelike, and sheared honeycomb lattices, triangular slices as well as trianglesuperlattices. This is of relevance for constructing templates that enforce crystal growth of unusual solidstructures.DOI: 10.1103/PhysRevE.65.041602 PACS number~s!: 67.70.1n, 82.70.Dd, 68.43.2h, 68.08.BcI. INTRODUCTION

The pair interaction between two stiff parallel linear DNA molecules depends not only on the distance between their axes but on their azimuthal orientation. The positional and orientational order in columnar B-DNA assemblies in solution is investigated, based on the DNA-DNA electrostatic pair potential that takes into account DNA helical symmetry and the amount and distribution of adsorbed counterions. A phase diagram obtained by lattice sum calculations predicts a variety of positionally and azimuthally ordered phases and bundling transitions strongly depending on the counterion adsorption patterns., Comment: 4 pages, 3 figures, submitted to PRL

The simulation of complex fluids naturally involves widely different length scales. Integrating out parts of the microscopic degrees of freedom leads to the concept of effective interactions and provides a “coarse-grained” picture which can be simulated much more efficiently than a full microscopic model. This approach bridges length scales in complex fluids. In this chapter, we justify this procedure on a Statistical Mechanics level and apply it to a variety of different systems ranging from charged colloidal dispersions and polymer solutions (including star polymers and dendrimers) to mixtures of colloids and polymers and binary colloidal mixtures. Problems arising when this concept is transferred to nano-scales are pointed out. Finally the much harder problem of bridging different time scales in complex fluids is briefly discussed.

Combining monomer-resolved molecular dynamics simulations with a theory based on a variational free energy, we calculate the conformational properties and the effective interactions of star-branched polyelectrolytes for a large variety of arm numbers, degrees of polymerization, and charge fractions, with and without added salt. We find quantitative agreement between theory and simulation and put forward analytical expressions that allow the calculation of the interaction between such macromolecules.

We investigate the system of D-dimensional hard spheres in D-dimensional space, where D.3. For the fluid phase of these hyperspheres, we generalize scaled-particle theory to arbitrary D and furthermore use the virial expansion and the Percus-Yevick integral equation. For the crystalline phase, we adopt cell theory based on elementary geometrical assumptions about close-packed lattices. Regardless of the approximation applied, and for dimensions as high as D550, we find a first-order freezing transition, which preempts the Kirkwood second-order instability of the fluid. The relative density jump increases with D, and a generalized Lindemann rule of melting holds. We have also used ideas from fundamental-measure theory to obtain a free energy density functional for hard hyperspheres. Finally, we have calculated the surface tension of a hypersphere fluid near a hard smooth ~hyper-!wall within scaled-particle theory.

We calculate the layer-resolved local fivefold symmetry of liquids near interfaces using computer simulation of hard sphere fluids on structured substrates. In the first few adjacent liquid layers, the presence of a surface suppresses local icosahedral packing while the magnitude of local fivefold symmetry in the next layers depends on details of the particle-substrate interaction. For a strong particle-substrate attraction, the local fivefold symmetry in these layers is higher than in the bulk liquid.

We study the effect of solvent granularity on the effective force between two charged colloidal particles by computer simulations of the primitive model of strongly asymmetric electrolytes with an explicitly added hard sphere solvent. Apart from molecular oscillating forces for nearly touching colloids which arise from solvent and counterion layering, the counterions are attracted towards the colloidal surfaces by solvent depletion providing a simple statistical description of hydration. This, in turn, has an important influence on the effective forces for larger distances which are considerably reduced as compared to the prediction based on the primitive model. When these forces are repulsive, the long-distance behaviour can be described by an effective Yukawa pair potential with a solvent-renormalized charge. As a function of colloidal volume fraction and added salt concentration, this solvent-renormalized charge behaves qualitatively similar to that obtained via the Poisson-Boltzmann cell model but there are quantitative differences. For divalent counterions and nano-sized colloids, on the other hand, the hydration may lead to overscreened colloids with mutual attraction while the primitive model yields repulsive forces. All these new effects can be accounted for through a solvent-averaged primitive model (SPM) which is obtained from the full model by integrating out the solvent degrees of freedom. The SPM was used to access larger colloidal particles without simulating the solvent explicitly., Comment: 14 pages, 16 craphics

Despite the large differences in mass, length and time scales, suspensions of spherical colloidal particles in a solvent share many features of simple atomic liquids, including structure, phase behaviour and even the transition to a glassy state at high concentrations. The analogies, but also the differences, will be illustrated by a few recent applications of the Statistical Mechanics formalism of simple liquids to sterically or charge-stabilized, concentrated colloidal suspensions. Examples include sedimentation equilibrium and non-linear screening of charged colloids by counterions.