Search results for "Hard spheres"
showing 10 items of 66 documents
Crystallization of hard spheres revisited. I. Extracting kinetics and free energy landscape from forward flux sampling
2018
We investigate the kinetics and the free energy landscape of the crystallization of hard spheres from a supersaturated metastable liquid though direct simulations and forward flux sampling. In this first paper, we describe and test two different ways to reconstruct the free energy barriers from the sampled steady state probability distribution of cluster sizes without sampling the equilibrium distribution. The first method is based on mean first passage times, and the second method is based on splitting probabilities. We verify both methods for a single particle moving in a double-well potential. For the nucleation of hard spheres, these methods allow us to probe a wide range of supersatura…
Exact results for the homogeneous cooling state of an inelastic hard-sphere gas
1998
The infinite set of moments of the two-particle distribution function is found exactly for the uniform cooling state of a hard-sphere gas with inelastic collisions. Their form shows that velocity correlations cannot be neglected, and consequently the 'molecular chaos' hypothesis leading to the inelastic Boltzmann and Enskog kinetic equations must be questioned. © 1998 Cambridge University Press.
Diffusion in concentrated colloidal suspensions and glasses
1998
The well established analogy between colloidal suspensions and atomic fluids has been extended to the glass transition problem in the past few years. Colloids have become the ideal test case for checking glass transition theories; this was due to the possibility of modeling hard spheres with colloidal dispersions. Significant progress has also been made in instrumentation, especially in the development of light-scattering techniques allowing moderately turbid and nonergodic samples to be analyzed. Mode coupling theory has become a paradigm not only for the glass transition, but also for the understanding of dynamics in highly concentrated colloidal dispersions where crystallization is suppr…
Phase behaviour of deionized binary mixtures of charged colloidal spheres.
2009
We review recent work on the phase behaviour of binary charged sphere mixtures as a function of particle concentration and composition. Both size ratios and charge ratios are varied over a wide range. By contrast to hard spheres the long ranged Coulomb interaction stabilizes the crystal phase at low particle concentrations and shifts the occurrence of amorphous solids to particle concentrations considerably larger than the freezing concentration. Depending on size- and charge ratios we observe upper azeotrope, spindle, lower azeotrope and eutectic types of phase diagrams, all known well from metal systems. Most solids are of body centred cubic structure. Occasionally stoichiometric compound…
On the derivation of a linear Boltzmann equation from a periodic lattice gas
2004
We consider the problem of deriving the linear Boltzmann equation from the Lorentz process with hard spheres obstacles. In a suitable limit (the Boltzmann-Grad limit), it has been proved that the linear Boltzmann equation can be obtained when the position of obstacles are Poisson distributed, while the validation fails, also for the "correct" ratio between obstacle size and lattice parameter, when they are distributed on a purely periodic lattice, because of the existence of very long free trajectories. Here we validate the linear Boltzmann equation, in the limit when the scatterer's radius epsilon vanishes, for a family of Lorentz processes such that the obstacles have a random distributio…
Phase separation in multi-component mixtures: the four-component case
2002
Abstract Calculation of ternary phase diagrams for several mixtures formed by two salts and a neutral component is presented here. The phase diagrams are obtained by inspection of the shape of the Gibbs free energy of mixing surface (Gmix) as a function of the composition at constant temperature and pressure. The Gmix surface is calculated by the mean spherical approximation (MSA). The model for the mixtures is represented by hard spheres, with the charged components interacting via a Coulomb potential. The results are interpreted in terms of a thermodynamic analysis of the contributions to the Gibbs free energy of mixing, i.e., the configurational energy, the volume and the entropy of mixi…
Polydisperse hard spheres: crystallization kinetics in small systems and role of local structure
2016
We study numerically the crystallization of a hard-sphere mixture with 8\% polydispersity. Although often used as a model glass former, for small system sizes we observe crystallization in molecular dynamics simulations. This opens the possibility to study the competition between crystallization and structural relaxation of the melt, which typically is out of reach due to the disparate timescales. We quantify the dependence of relaxation and crystallization times on density and system size. For one density and system size we perform a detailed committor analysis to investigate the suitability of local structures as order parameters to describe the crystallization process. We find that local…
Hard-Core Thinnings of Germ‒Grain Models with Power-Law Grain Sizes
2013
Random sets with long-range dependence can be generated using a Boolean model with power-law grain sizes. We study thinnings of such Boolean models which have the hard-core property that no grains overlap in the resulting germ‒grain model. A fundamental question is whether long-range dependence is preserved under such thinnings. To answer this question, we study four natural thinnings of a Poisson germ‒grain model where the grains are spheres with a regularly varying size distribution. We show that a thinning which favors large grains preserves the slow correlation decay of the original model, whereas a thinning which favors small grains does not. Our most interesting finding concerns the c…
Growth of a colloidal crystallite of hard spheres
1997
Abstract We examine the growth of a single nucleus of hard spheres in a super-saturated colloidal dispersion of hard spheres. A model developed by Bruce Ackerson and Klaus Schatzel based on a Wilson-Frenkel growth law is used. Our emphasis is on the profile of the radial density distribution around the growing (but still spherically symmetric) grain and its Fourier transform, the grain's form factor, which can be observed under small scattering angles in a dynamic light scattering experiment. Depending on the value of the supersaturation we can identify two limiting cases of different growth exponents and density profiles: one is the Frank theory of diffusion-limited growth and the other is…
Solidification kinetics of hard-sphere colloidal suspensions
2007
We investigate the solidification dynamics of hard-sphere colloidal suspensions applying simultaneously small-angle and Bragg light scattering. These experiments allow a consistent picture of nucleation and crystal growth on the level of large-scale density fluctuations and of density fluctuations on the level of individual crystallites. We observe a temporally almost constant nucleation rate after an induction time that decreases with supersaturation. The classical expectation for the nucleation rate density as a function of supersaturation is in accordance with our data. We investigate the validity of the Wilson—Frenkel growth law for hard-sphere systems, which also fits our data satisfac…