Hard-sphere System Research Articles

Ordered and disordered stealthy hyperuniform point patterns across spatial dimensions

In previous work [] it was shown that stealthy hyperuniform systems can be regarded as hard spheres in Fourier space in the sense that the structure factor is exactly zero in a spherical region around the origin in analogy with the pair-correlation function of real-space hard spheres. While this earlier work focused on spatial dimensions d=1–4, here we extend the analysis to higher dimensions in order to make connections to high-dimensional sphere packings and the mean-field theory of glasses. We exploit this correspondence to confirm that the densest Fourier-space hard-sphere system is that of a Bravais lattice in contrast to real-space hard spheres, whose densest configuration is conjectured to be disordered. In passing, we give a concise form for the position of the first Bragg peak. We also extend the virial series previously suggested for disordered stealthy hyperuniform systems to higher dimensions in order to predict spatial decorrelation as a function of dimension. This prediction is then borne out by numerical simulations of disordered stealthy hyperuniform ground states in dimensions d=2–8, which have only recently been made possible due to a highly parallelized algorithm. Published by the American Physical Society 2024

Hole statistics of equilibrium 2D and 3D hard-sphere crystals.

The probability of finding a spherical "hole" of a given radius r contains crucial structural information about many-body systems. Such hole statistics, including the void conditional nearest-neighbor probability functions GV(r), have been well studied for hard-sphere fluids in d-dimensional Euclidean space Rd. However, little is known about these functions for hard-sphere crystals for values of r beyond the hard-sphere diameter, as large holes are extremely rare in crystal phases. To overcome these computational challenges, we introduce a biased-sampling scheme that accurately determines hole statistics for equilibrium hard spheres on ranges of r that far extend those that could be previously explored. We discover that GV(r) in crystal and hexatic states exhibits oscillations whose amplitudes increase rapidly with the packing fraction, which stands in contrast to GV(r) that monotonically increases with r for fluid states. The oscillations in GV(r) for 2D crystals are strongly correlated with the local orientational order metric in the vicinity of the holes, and variations in GV(r) for 3D states indicate a transition between tetrahedral and octahedral holes, demonstrating the power of GV(r) as a probe of local coordination geometry. To further study the statistics of interparticle spacing in hard-sphere systems, we compute the local packing fraction distribution f(ϕl) of Delaunay cells and find that, for d ≤ 3, the excess kurtosis of f(ϕl) switches signat a certain transitional global packing fraction. Our accurate methods to access hole statistics in hard-sphere crystals at the challenging intermediate length scales reported here can be applied to understand the important problem of solvation and hydrophobicity in water at such length scales.

Ising Paradigm in Isobaric Ensembles.

We review recent work on Ising-like models with "compressible cells" of fluctuating volume that, as such, are naturally treated in NpT and μpT ensembles. Besides volumetric phenomena, local entropic effects crucially underlie the models. We focus on "compressible cell gases" (CCG), namely, lattice gases with fluctuating cell volumes, and "compressible cell liquids" (CCL) with singly occupied cells and fluctuating cell volumes. CCGs contemplate singular diameters and "Yang-Yang features" predicted by the "complete scaling" formulation of asymmetric fluid criticality, with a specific version incorporating "ice-like" hydrogen bonding further describing the "singularity-free scenario" for the low-temperature unusual thermodynamics of supercooled water. In turn, suitable CCL variants constitute adequate prototypes of water-like liquid-liquid criticality and the freezing transition of a system of hard spheres. On incorporating vacant cells to such two-state CCL variants, one obtains three-state, BEG-like models providing a satisfactory description of water's "second-critical-point scenario" and the whole phase behavior of a simple substance like argon. Future challenges comprise water's crystal-fluid phase behavior and metastable states.

Statistical theory of fluids confined in quenched disordered porous media.

We develop a theory to calculate structural correlations and thermodynamic properties of a fluid confined in a random porous solid medium (matrix). We used density functional formalism to derive an annealed averaged expression for the density profile and excess free energy of fluid arising due to random fields of a particular realization of the matrix. After performing the second average over the quenched-disordered variables, the excess free energy is organized to give one- and two-body potentials for fluid particles. The average over disorder reduces the system to an effective one-component system of fluid in which particles feel one-body (external) potential and interact via effective pair potential. The effective pair potential is a sum of the bare (the one in the pure fluid) and the matrix-induced potential. The resulting partition function involves only fluid variables. Equations are derived for fluid-fluid and fluid-matrix correlation functions and for free energy, pressure, and chemical potential of the fluid. The theory is applied to a model system of hard spheres and results for the effective pair potential, correlation functions, and thermodynamic properties are reported. The effective pair potential is found to be attractive at the contact and develops a repulsive peak before decaying to zero. Results for pair correlation function and structure factor are compared with simulation results for several fluid densities at two matrix densities. In all the cases, a very good agreement has been found.

Phase transition face-centered cubic crystal — homogeneous phase in helium

In this work, the characteristics of the phase transition face-centered cubic crystal — homogeneous phase in helium are calculated based on the correlation cell-cluster expansion. The theoretical data were compared with experimental data and good agreement was obtained. It is discussed the use of data on phase transitions in helium to estimate thermodynamic characteristics phase transition in a quantum system of hard spheres.

Modeling order–disorder boundaries of colloidal dispersions in organic solvents using interaction force measurements

HypothesisThe formation of soft colloidal crystals, which are nonclose-packed ordered arrays of colloidal particles suspended in a solvent, is dictated by a single physical factor that yields a fixed threshold at order–disorder boundaries for different experimental conditions such as ion concentration, solvent type, and particle size. Identifying the determinant factor and its threshold value should enable the prediction of the critical concentrations of colloidal particles to form soft colloidal crystals. ExperimentsSoft colloidal crystals were fabricated using a series of monohydric alcohols as dispersion media and reflectance spectra were measured to locate order–disorder boundaries. The interaction forces acting between particles were also measured by employing atomic force microscopy. FindingsThe interparticle forces at the order–disorder boundaries exhibited a universal threshold that was independent of the solvent types including alcohols and water. Therefore, the determinant factor for the formation of soft colloidal crystals was determined to be the force acting between the particles. Furthermore, a priori calculation of this critical force and consequently the critical particle concentration in colloidal systems was demonstrated by referring to the pressure at the liquid-to-solid transition in a hard sphere system (Alder transition).

Hydrodynamic correlation and spectral functions of perfect cubic crystals

We investigate the collective dynamics of the perfect cubic crystal by deriving from the hydrodynamic equations the time-dependent correlation and the spectral functions characterizing the fluctuations of mass and momentum densities. We show that the seven hydrodynamic modes of the perfect crystal can be identified from the resonances of these spectral functions. The comparison with those of a fluid is discussed. Using the numerical values of the thermodynamic, elastic, and transport coefficients computed in our previous paper (J Mabillard and P Gaspard 2024 J. Stat. Mech. 023208) for a system of hard spheres, the theoretical expressions for the correlation and spectral functions are compared to the same functions directly computed using molecular dynamics simulations. The excellent agreement between theory and simulation provides strong support for the microscopic hydrodynamic theory of perfect crystals based on the local-equilibrium approach. This work sheds light on the fundamental mechanisms governing the collective behavior of matter in the solid state.

Diffusion dynamics for an infinite system of two-type spheres and the associated depletion effect

We consider a random diffusion dynamics for an infinite system of hard spheres of two different sizes evolving in Rd, its reversible probability measure, and its projection on the subset of the large spheres. The main feature is the occurrence of an attractive short-range dynamical interaction – known in the physics literature as a depletion interaction – between the large spheres, which is induced by the hidden presence of the small ones. By considering the asymptotic limit for such a system when the density of the particles is high, we also obtain a constructive dynamical approach to the famous discrete geometry problem of maximising the contact number of n identical spheres in Rd. As support material, we propose numerical simulations in the form of movies.

Emergence of directed motion in a crowded suspension of overdamped particles with different effective temperatures

In this work, we focus on the behavior of a single passive Brownian particle in a suspension of passive particles with short-range repulsive interactions and higher effective temperature. While the forces affecting the single particle are thermal-like fluctuations and repulsion, due to other particles in the suspension, our numerical simulations show that on intermediate timescales directed motion on a single-particle level emerges. This emergent directional motion leads to a breakdown of the Einstein relation and nonmonotonic augmentation of the measured diffusion coefficient. Directional tendency increases with the density of the suspension and leads to growth of the diffusivity with the density of the suspension, a phenomenon recently observed for a system of hard spheres by Ilker, Castellana, and Joanny. Counterintuitively, the directional flow originates from the tendency of different particles to push each other out of their way. Due to such strictly repulsive interactions, nearby particles form into temporally correlated pairs and move cooperatively, thus creating a preferred direction of motion on intermediate timescales. We show that directional motion emerges when the ratio of the effective temperatures of the tracked particle and suspension constituents is below a critical value. Published by the American Physical Society 2024

Radial Distribution Function of Hard Spheres at Different Densities

The model of hard sphere system has important part in modern theories of liquids. Hard sphere fluid is considered as the most intensively studied system among all model fluids. The thermodynamic and structural properties of real fluids can be studied with the help of hard spheres fluid. The exact solution of Ornstein-Zernike (OZ) equation with Percus-Yevick (PY) along with the equation of state provides an approximate analytical expression for radial distribution function (RDF). This work intends to study the radial distribution function of Hard sphere (HS) using the PY approximation for different densities ranging from low to high to find out their structural properties, packing behavior, phase transitions, and thermodynamics. We use FORTRAN program for this purpose. At low densities, the RDF has a single peak at a distance corresponding to the hard sphere diameter, indicating that the particles are well- separated and not interacting with each other like gaseous. As density increases, the peak becomes broader and shifts to smaller distances, indicating that the particles are coming into closer contact and interacting more strongly with each other. The height of the peak also increases, indicating that there is a greater probability of finding a particle at a certain distance from another particle.

The Guggenheim equation for a system of hard spheres and its generalization

In the present work, for the first time, the generalized Guggenheim equation for a system of hard spheres is obtained based on the use of the Euler accelerated convergence method. This equation allows taking into account an arbitrary number of known virial coefficients. For a metastable region, this equation is generalized to the case of taking into account the asymptotic behavior of the free energy at high densities. The resulting expression for the compressibility of the homogeneous phase of a system of hard spheres describes the data of a numerical experiment within their accuracy.

O teploemkosti kvantovoy sistemy tverdykh sfer

The thermodynamic properties of the Boltzmann hard sphere system is discussed. It was found that zero point energy decreases with temperature so slowly that it turned out to be an almost a constant addition to the classical value. In result the heat capacity of the system differs little from the classical value of 3/2 k everywhere except for the narrow region of low temperatures, where heat capacity drops to zero. The predicted linear temperature contribution to the heat capacity like in ideal Fermi gas was clearly detected in the quantum hard sphere system at the lowest temperatures.

Guggenheim Equation for a System of Hard Spheres and Its Generalization

Guggenheim Equation for a System of Hard Spheres and Its Generalization

Local stability of spheres via the convex hull and the radical Voronoi diagram.

Jamming is an emergent phenomenon wherein the local stability of individual particles percolates to form a globally rigid structure. However, the onset of rigidity does not imply that every particle becomes rigid, and indeed some remain locally unstable. These particles, if they become unmoored from their neighbors, are called rattlers, and their identification is critical to understanding the rigid backbone of a packing, as these particles cannot bear stress. The accurate identification of rattlers, however, can be a time-consuming process, and the currently accepted method lacks a simple geometric interpretation. In this manuscript, we propose two simpler classifications of rattlers in hard sphere systems based on the convex hull of contacting neighbors and the maximum inscribed sphere of the radical Voronoi cell, each of which provides geometric insight into the source of their instability. Furthermore, the convex hull formulation can be generalized to explore stability in hyperstatic soft sphere packings, spring networks, nonspherical packings, and mean-field non-central-force potentials.

Modeling the structure and thermodynamics of multicomponent and polydisperse hard-sphere dispersions with continuous potentials.

A model system of identical particles interacting via a hard-sphere potential is essential in condensed matter physics; it helps to understand in and out of equilibrium phenomena in complex fluids, such as colloidal dispersions. Yet, most of the fixed time-step algorithms to study the transport properties of those systems have drawbacks due to the mathematical nature of the interparticle potential. Because of this, mapping a hard-sphere potential onto a soft potential has been recently proposed [Báez et al., J. Chem. Phys. 149, 164907 (2018)]. More specifically, using the second virial coefficient criterion, one can set a route to estimate the parameters of the soft potential that accurately reproduces the thermodynamic properties of a monocomponent hard-sphere system. However, real colloidal dispersions are multicomponent or polydisperse, making it important to find an efficient way to extend the potential model for dealing with such kind of many-body systems. In this paper, we report on the extension and applicability of the second virial coefficient criterion to build a description that correctly captures the phenomenology of both multicomponent and polydisperse hard-sphere dispersions. To assess the accuracy of the continuous potentials, we compare the structure of soft polydisperse systems with their hard-core counterpart. We also contrast the structural and thermodynamic properties of soft binary mixtures with those obtained through mean-field approximations and the Ornstein-Zernike equation for the two-component hard-sphere dispersion.

Influence of friction on the packing efficiency and short-to-intermediate range structure of hard-sphere systems.

Using particle-resolved computer simulations, we investigate the effect of friction on the packing structure of hard-sphere mixtures with two kinds of particles under external compression. We first show that increasing friction between the particles results in a more disordered and less efficient packing of the local structure on the nearest neighbor scale. It is also found that standard two-point correlation functions, i.e., radial distribution function and static structure factor, show basically no detectable changes beyond short-range distances upon varying inter-particle friction. Further analysis of the structure using a four-point correlation method reveals that these systems have on the intermediate-range scale a three-dimensional structure with an icosahedral/dodecahedral symmetry that exhibits a pronounced dependence on friction: small friction gives rise to an orientational order that extends to larger distances. Our results also demonstrate that composition plays a role in that the degree of structural order and the structural correlation length are mainly affected by the friction coefficients associated with the more abundant species.

On melting of Boltzmann system of quantum hard spheres.

Melting of a quantum system of hard spheres has been considered in the case when the effects of Bose and Fermi statistics can be neglected. It has been found that the quantum melting line always differs from the classical line except for T = 0, P = 0, where the both lines cross. It is shown that the classical limit is not reachable at any finite temperature.

Geometric conjecture about phase transitions.

As phenomena that necessarily emerge from the collective behavior of interacting particles, phase transitions continue to be difficult to predict using statistical thermodynamics. A recent proposal called the topological hypothesis suggests that the existence of a phase transition could perhaps be inferred from changes to the topology of the accessible part of the configuration space. This paper instead suggests that such a topological change is often associated with a dramatic change in the configuration space geometry, and that the geometric change is the actual driver of the phase transition. More precisely, a geometric change that brings about a discontinuity in the mixing time required for an initial probability distribution on the configuration space to reach the steady state is conjectured to be related to the onset of a phase transition in the thermodynamic limit. This conjecture is tested by evaluating the diffusion diameter and ε-mixing time of the configuration spaces of hard-disk and hard-sphere systems of increasing size. Explicit geometries are constructed for the configuration spaces of these systems and numerical evidence suggests that a discontinuity in the ε-mixing time coincides with the solid-fluid phase transition in the thermodynamic limit.

Derivation of a macroscopic model for Brownian hard needles

We study the role of anisotropic steric interactions in a system of hard Brownian needles in two dimensions. Despite having no volume, non-overlapping needles exclude a volume in configuration space that influences the macroscopic evolution of the system. Starting from the stochastic particle system, we use the method of matched asymptotic expansions and conformal mapping to systematically derive a nonlinear non-local partial differential equation for the evolution of the population density in position and orientation. We consider the regime of high rotational diffusion, resulting in an equation for the spatial density that allows us to compare the effective excluded volume of a hard-needle system with that of a hard-sphere system. We further consider spatially homogeneous solutions and find an isotropic to nematic transition as density increases, consistent with Onsager’s theory.

Dynamics and Time Scales of Higher-Order Correlations in Supercooled Colloidal Systems.

The dynamics and time scales of higher-order correlations are studied in supercooled colloidal systems. A combination of X-ray photon correlation spectroscopy (XPCS) and X-ray cross-correlation analysis (XCCA) shows the typical slowing of the dynamics of a hard sphere system when approaching the glass transition. The time scales of higher-order correlations are probed using a novel time correlation function gC, tracking the time evolution of cross-correlation function C. With an increasing volume fraction, the ratio of relaxation times of gC to the standard individual particle relaxation time obtained by XPCS increases from ∼0.4 to ∼0.9. While a value of ∼0.5 is expected for free diffusion, the increasing values suggest that the local orders within the sample are becoming more long-lived for larger volume fractions. Furthermore, the dynamics of local order is more heterogeneous than the individual particle dynamics. These results indicate that not only the presence but also the lifetime of locally favored structures increases close to the glass transition.