Entropic Identification of the First Order Freezing Transition of a Suspension of Hard Sphere Particles.

We analyze the experimental particle current autocorrelation function of suspensions of hard spheres. Interactions between the particles are mediated by thermally activated acoustic excitations in the solvent. Those acoustic modes are tantamount to the system's (energy) microstates and by their orthogonality, each of those modes can be identified with an independent Brownian particle current. Accordingly, partitioning of the system's energy states is impressed on the current autocorrelation function. This impression provides a novel measure of the entropy and location of a partitioning or entropy limit at a packing fraction that coincides with that of the observed suspension's first order freezing transition.

Coincidence of the freezing and the onset of caging in hard sphere and Lennard-Jones fluids.

In this article, we examine the collective particle dynamics, as expressed by the time correlation function of the longitudinal particle current density, of several different fluids in the vicinity of their freezing points/lines. We consider and compare results obtained by dynamic light scattering for a suspension of hard spheres and by molecular dynamics for fluids with hard sphere and Lennard-Jones interactions. The latter are performed along both an isotherm and an isochore. In all cases, we find a qualitative change in the collective dynamics, within the resolution of the data, when their respective freezing lines are crossed. We associate this change with the onset of caging. The new results for the Lennard-Jones fluid reported here confirm that the occurrence of caging, found previously for systems of hard spheres, is a more general feature that distinguishes a metastable fluid from one in thermodynamic equilibrium.

The cage effect in systems of hard spheres.

The cage effect is generally invoked when discussing the delay in the decay of time correlation functions of dense fluids. In an attempt to examine the role of caging more closely, we consider the spread of the displacement distributions of Brownian particles. These distributions are necessarily biased by the presence of neighbouring particles. Accommodation of this bias by those neighbours conserves the displacement distribution locally and presents a collective mechanism for exploring configuration space that is more efficient than the intrinsic Brownian motion. Caging of some particles incurs, through the impost of global conservation of the displacement distribution, a delayed, non-local collective process. This non-locality compromises the efficiency with which configuration space is explored. Both collective mechanisms incur delay or stretching of time correlation functions, in particular the particle number and flux densities. This paper identifies and distinguishes these mechanisms in existing data from experiments and computer simulations on systems of particles with hard sphere interactions.

Charged colloidal model systems under confinement in slit geometry: a new setup for optical microscopic studies.

A new experimental setup for optical microscopic studies of charged colloidal model systems under confinement between two flat walls is presented. The measurement cell consists of optically flat quartz substrates attached to piezo actuators. Those facilitate fast and flexible adjustment of the confining geometry. Optionally, the local cell height can be quantitatively controlled by in situ interferometric measurements. Proper choice of materials guarantees sufficient chemical inertia against contamination with salt ions. For efficient preparation of charged colloidal suspensions under strongly deionized conditions, the cell can be connected to a conventional pump circuit including a mixed bed ion exchanger column. The usefulness of this setup, in particular for investigating the equilibrium phase behavior of colloids at low background salt concentrations, is demonstrated recalling recent experiments.

Crystalline multilayers of charged colloids in soft confinement: experiment versus theory.

We combine real-space experiments and lattice sum calculations to investigate the phase diagram of charged colloidal particles under soft confinement. In the experiments we explore the equilibrium phase diagram of charged colloidal spheres in aqueous suspensions confined between two parallel charged walls at low background salt concentrations. Motivated by the experiments, we perform lattice sum minimizations to predict the crystalline ground state of point-like Yukawa particles which are exposed to a soft confining wall potential. In the multilayered crystalline regime, we obtain good agreement between the experimental and numerical findings: upon increasing the density we recover the sequence [structure: see text].

Colloidal crystallization in the quasi-two-dimensional induced by electrolyte gradients.

We investigated driven crystal formation events in thin layers of sedimented colloidal particles under low salt conditions. Using optical microscopy, we observe particles in a thermodynamically stable colloidal fluid to move radially converging towards cation exchange resin fragments acting as seed particles. When the local particle concentration has become sufficiently large, subsequently crystallization occurs. Brownian dynamics simulations of a 2D system of purely repulsive point-like particles exposed to an attractive potential, yield strikingly similar scenarios, and kinetics of accumulation and micro-structure formation. This offers the possibility of flexibly designing and manufacturing thin colloidal crystals at controlled positions and thus to obtain specific micro-structures not accessible by conventional approaches. We further demonstrate that particle motion is correlated with the existence of a gradient in electrolyte concentration due to the release of electrolyte by the seeds.

Crystallization in suspensions of hard spheres: a Monte Carlo and molecular dynamics simulation study.

The crystallization of a metastable melt is one of the most important non-equilibrium phenomena in condensed matter physics, and hard sphere colloidal model systems have been used for several decades to investigate this process by experimental observation and computer simulation. Nevertheless, there is still an unexplained discrepancy between the simulation data and experimental nucleation rate densities. In this paper we examine the nucleation process in hard spheres using molecular dynamics and Monte Carlo simulation. We show that the crystallization process is mediated by precursors of low orientational bond-order and that our simulation data fairly match the experimental data sets.

Precursor-mediated crystallization process in suspensions of hard spheres.

We report on a large scale computer simulation study of crystal nucleation in hard spheres. Through a combined analysis of real- and reciprocal-space data, a picture of a two-step crystallization process is supported: First, dense, amorphous clusters form which then act as precursors for the nucleation of well-ordered crystallites. This kind of crystallization process has been previously observed in systems that interact via potentials that have an attractive as well as a repulsive part, most prominently in protein solutions. In this context the effect has been attributed to the presence of metastable fluid-fluid demixing. Our simulations, however, show that a purely repulsive system (that has no metastable fluid-fluid coexistence) crystallizes via the same mechanism.

Preparation and characterization of particles with small differences in polydispersity.

Colloidal particles are widely used both in fundamental research and in materials science. One important parameter influencing the physical properties of colloidal materials is the particle size distribution (polydispersity) of the colloidal particles. Recent work on colloidal crystallization has demonstrated that even subtle changes in polydispersity can have significant effects. In this study we present centrifugation techniques for subtly manipulating the width and the shape of the particle size distribution, for polydispersities less than 10%. We use scanning electron microscopy as well as dynamic and static light scattering to characterize the particle size distributions. We compare the results and highlight the difficulties associated with the determination of accurate particle size distributions.

Fast microscopic method for large scale determination of structure, morphology, and quality of thin colloidal crystals.

We present a novel fast microscopic method to analyze the crystal structures of air-dried or suspended colloidal multilayer systems. Once typical lattice spacings of such films are in the range of visible light, characteristic Bragg scattering patterns are observed. If in microscopic observations these are excluded from image construction, a unique color coding for regions of different structures, morphologies, and layer numbers results. Incoherently scattering defect structures, however, may not be excluded from image construction and thus remain visible with high resolution.