Application of the scaled particle theory to the glass transition of hard spheres

In a previous article [1], an improved approach to the scaled particle theory of Reiss et al. was presented. As a result, we obtained a Padé-like expression of the compressibility factor of the fluid state. That expression contains two parameters p ₁ and p ₂, which we were able to calculate. In this paper we find other sets of values for p ₁ and p ₂. Two of these sets yield equations of state which agree with the simulation results of the glassy states obtained by Woodcock and Speedy. The calculations are based on two assumptions: firstly, that second order phase transitions may occur and secondly, that a hard sphere glass contains a fluid-like and a solid-like part. As an additional result, we found an upper and a lower limit for the fluid densities at which glass transitions may occur.     

Phase transition in gas of hard core spheres

We present a new method of analyzing the gas of hard core spheres. We investigate analytic properties of the thermodynamic function over the circle of convergence of the cluster expansion and describe the way in which phase transition occurs.     

Signatures of glass formation in a fluidized bed of hard spheres

We demonstrate that a fluidized bed of hard spheres during defluidization displays properties associated with formation of a glass. The final state is rate dependent, and as this state is approached, the bed exhibits heterogeneity with increasing time and length scales. The formation of a glass results in the arrest of macroscopic particle motion and thus the loss of fluidization. Microscopic motion persists in this state, but the bed can be jammed by application of a small increase in flow rate. Thus a fluidized bed can serve as a test system for studies of glass formation and jamming.     

Is the percolation transition of hard spheres a thermodynamic phase transition?

In hard-sphere systems, there is a fluid-solid transition, but no gas-liquid transition. In the fluid region, however, one can find a purely geometric percolation transition, which is studied in detail. The van der Waals model of hard spheres is treated. In this model, a uniform negative background potential is added. This modification does not change the structure, but induces a gas-liquid transition. In fact, percolation and the gas-liquid transition can be related to each other.     

Glass transition line for the system of charged hard spheres

We locate the glass transition line of the charged-hard-sphere system in the density-temperature plane, using a mean-field hypernetted chain approximation within the replica-symmetry-breaking scenario [S. Franz and G. Parisi, Phys. Rev. Lett. 79 (1997) 2486. [11]]. Our results demonstrate a dominant role of the steric factor and explain the ineffectiveness of purely Coulombic interactions in driving phase transitions.     

Mixtures of hard spherocylinders and hard spheres

Monte Carlo simulations have been performed for equimolar mixtures of hard prolate spherocylinders of length: breadth ratio 2:1 and hard spheres, in the fluid region. Two systems have been studied. In the first the breadth of the spherocylinder was equal to the hard sphere diameter, and in the second system both components were of equal molecular volume.

The compressibility factor, PV/NkT, has been obtained for both mixtures at four reduced densities (packing fractions) from 0·20 to 0·45. The results have been compared with the predictions of several analytical equations appropriate to mixtures of hard convex molecules, and an equation due to Pavlicek et al. was found to be very accurate. The results have been used to calculate the excess volumes of mixing at constant pressure, in an attempt to establish the relative importance of the effects of differences in molecular volume and shape on the thermodynamic properties.

The structural properties of the mixtures have also been investigated by calculating pair distribution functions for the three types of pair interactions present in these mixtures.     

A first-order phase transition defines the random close packing of hard spheres

Randomly packing spheres of equal size into a container consistently results in a static configuration with a density of ∼64%. The ubiquity of random close packing (RCP) rather than the optimal crystalline array at 74% begs the question of the physical law behind this empirically deduced state. Indeed, there is no signature of any macroscopic quantity with a discontinuity associated with the observed packing limit. Here we show that RCP can be interpreted as a manifestation of a thermodynamic singularity, which defines it as the “freezing point” in a first-order phase transition between ordered and disordered packing phases. Despite the athermal nature of granular matter, we show the thermodynamic character of the transition in that it is accompanied by sharp discontinuities in volume and entropy. This occurs at a critical compactivity, which is the intensive variable that plays the role of temperature in granular matter. Our results predict the experimental conditions necessary for the formation of a jammed crystal by calculating an analogue of the “entropy of fusion”. This approach is useful since it maps out-of-equilibrium problems in complex systems onto simpler established frameworks in statistical mechanics.     

New mean-field theories for the liquid–vapour transition of charged hard spheres

The phase behaviour of the primitive model of electrolytes is studied in the framework of the various mean-field approximations obtained recently by means of methods pertaining to statistical field theory (J.-M. Caillol, J. statist. Phys., 115, 1461 (2004); extended version: arXiv:cond-mat/0305465). The role of the regularization of the Coulomb potential at short distances is discussed in detail and the link to more traditional approximations of the theory of liquids is discussed. The values computed for the critical temperatures, chemical potentials, and densities are compared with available Monte Carlo data and other theoretical predictions.     

Kinetic theory of hard spheres

Kinetic equations for the hard-sphere system are derived by diagrammatic techniques. A linear equation is obtained for the one-particle-one particle equilibrium time correlation function and a nonlinear equation for the one-particle distribution function in nonequilibrium. Both equations are nonlocal, noninstantaneous, and extremely complicated. They are valid for general density, since statistical correlations are taken into account systematically. This method derives several known and new results from a unified point of view. Simple approximations lead to the Boltzmann equation for low densities and to a modified form of the Enskog equation for higher densities.     

Colour conductivity of hard spheres

We present an analytic solution for the d-dimensional (d > 1) hard-sphere free flight trajectories in a thermostatted colour field. The solution shows that particles can only reach a finite distance in the direction perpendicular to the field in the absence of collisions. Using a numerical algorithm we designed to simulate many-body hard-sphere systems with curved trajectories, we study the onset of the instability leading to phase separation in the two-dimensional case for a range of field strengths and three densities. For the two fluid densities we find that phase separation occurs for sufficiently strong fields regardless of the initial configuration, and that the phase-separated state eventually becomes a collisionless, non-ergodic steady state. For solid densities the phase-separated configuration is stable and conducting, but is not an attractor for other charge distributions because of the impossibility of particle rearrangement.     

Dissipative dynamics for hard spheres

The dynamics for a system of hard spheres with dissipative collisions is described at the levels of statistical mechanics, kinetic theory, and simulation. The Liouville operator(s) and associated binary scattering operators are defined as the generators for time evolution in phase space. The BBGKY hierarchy for reduced distribution functions is given, and an approximate kinetic equation is obtained that extends the revised Enskog theory to dissipative dynamics. A Monte Carlo simulation method to solve this equation is described, extending the Bird method to the dense, dissipative hard-sphere system. A practical kinetic model for theoretical analysis of this equation also is proposed. As an illustration of these results, the kinetic theory and the Monte Carlo simulations are applied to the homogeneous cooling state of rapid granular flow.     

Equilibrium fluid-solid coexistence of hard spheres

We present a tethered Monte Carlo simulation of the crystallization of hard spheres. Our method boosts the traditional umbrella sampling to the point of making practical the study of constrained Gibbs' free energies depending on several crystalline order parameters. We obtain high-accuracy estimates of the fluid-crystal coexistence pressure for up to 2916 particles (enough to accommodate fluid-solid interfaces). We are able to extrapolate to infinite volume the coexistence pressure [p(co)=11.5727(10)k(B)T/σ(3)] and the interfacial free energy [γ({100})=0.636(11)k(B)T/σ(2)].     

Apparent viscosity and particle pressure of a concentrated suspension of non-Brownian hard spheres near the jamming transition

We consider the steady shear flow of a homogeneous and dense assembly of hard spheres suspended in a Newtonian viscous fluid. In a first part, a mean-field approach based on geometric arguments is used to determine the viscous dissipation in a dense isotropic suspension of smooth hard spheres and the hydrodynamic contribution to the suspension viscosity. In a second part, we consider the coexistence of transient solid clusters coupled to regions with free flowing particles near the jamming transition. The fraction of particles in transient clusters is derived through the Landau-Ginzburg concepts for first-order phase transition with an order parameter corresponding to the proportion of “solid” contacts. A state equation for the fraction of particle-accessible volume is introduced to derive the average normal stresses and a constitutive law that relates the total shear stress to the shear rate. The analytical expression of the average normal stresses well accounts for numerical or experimental evaluation of the particle pressure and non-equilibrium osmotic pressure in a dense sheared suspension. Both the friction level between particles and the suspension dilatancy are shown to determine the singularity of the apparent shear viscosity and the flow stability near the jamming transition. The model further predicts a Newtonian behavior for a concentrated suspension of neutrally buoyant particles and no shear thinning behavior in relation with the shear liquefaction of transient solid clusters.