Based on results from the physics and mathematics literature which suggest a series of clearly defined conjectures, we formulate three simple scenarios for the fate of hard sphere crystallization in high dimension: (A) crystallization is impeded and the glass phase constitutes the densest packing, (B) crystallization from the liquid is possible, but takes place much beyond the dynamical glass transition and is thus dynamically implausible, or (C) crystallization is possible and takes place before (or just after) dynamical arrest, thus making it plausibly accessible from the liquid state. In order to assess the underlying conjectures and thus obtain insight into which scenario is most likely to be realized, we investigate the densest sphere packings in dimension $d=3$-$10$ using cell-cluster expansions as well as numerical simulations. These resulting estimates of the crystal entropy near close-packing tend to support scenario C. We additionally confirm that the crystal equation of state is dominated by the free volume expansion and that a meaningful polynomial correction can be formulated.
The study on the relationship between the spheres and voids in packing system suggests that the edge effect at the interface between the container and the particles is an important factor lowering the packing ratio. To pack spheres in a container with high packing ratio, an optimized sphere size and an optimized sequence of sphere sizes exist for the packing of single-sized and multi-sized spheres, respectively. We suggest that the concepts of volume and contact should be clearly defined for the packing problem in specific scale.
In this paper we study the hard sphere packing problem in the Hamming space by the cavity method. We show that both the replica symmetric and the replica symmetry breaking approximations give maximum rates of packing that are asymptotically the same as the lower bound of Gilbert and Varshamov. Consistently with known numerical results, the replica symmetric equations also suggest a crystalline solution, where for even diameters the spheres are more likely to be found in one of the subspaces (even or odd) of the Hamming space. These crystalline packings can be generated by a recursive algorithm…
We computationally study jammed disordered hard-sphere packings as large as a million particles. We show that the packings are saturated and hyperuniform, i.e., that local density fluctuations grow only as a logarithmically-augmented surface area rather than the volume of the window. The structure factor shows an unusual non-analytic linear dependence near the origin, $S(k)\sim|k|$. In addition to exponentially damped oscillations seen in liquids, this implies a weak power-law tail in the total correlation function, $h(r)\sim-r^{-4}$, and a long-ranged direct correlation function.
We analyze the large scale structure and fluctuations of jammed packings of size disperse spheres, produced in a granular experiment as well as numerically. While the structure factor of the packings reveals no unusual behavior for small wavevectors, the compressibility displays an anomalous linear dependence at low wavectors and vanishes when q -> 0. We show that such behavior occurs because jammed packings of size disperse spheres have no bulk fluctuations of the volume fraction and are thus hyperuniform, a property not observed experimentally before. Our results apply to arbitrary particle …
Heat conduction in a random packing of hard spheres is studied by nonequilibrium molecular dynamics simulation. We find a hard-sphere random packing shows higher thermal conductivity than a crystalline packing with same packing fraction. Under the same pressure, the random structure causes reduction of thermal conductivity by only 10% from crystalline packing, which is consistent with the experimental fact that amorphous materials can have high thermal conductivity which is comparable to that of crystals.
The notion of random close packings of a bulk static collection of ball bearings or sand grains was introduced in the 1960's by G.D. Scott and J.D. Bernal. There have been numerous attempts to understand the packings. We give a short argument, based on recent experiments and simulations, which explains the packings in purely geometric terms.
The densest binary sphere packings have historically been very difficult to determine. The only rigorously known packings in the alpha-x plane of sphere radius ratio alpha and relative concentration x are at the Kepler limit alpha = 1, where packings are monodisperse. Utilizing an implementation of the Torquato-Jiao sphere-packing algorithm [S. Torquato and Y. Jiao, Phys. Rev. E 82, 061302 (2010)], we present the most comprehensive determination to date of the phase diagram in (alpha,x) for the densest binary sphere packings. Unexpectedly, we find many distinct new densest packings.
Despite its long history, there are many fundamental issues concerning random packings of spheres that remain elusive, including a precise definition of random close packing (RCP). We argue that the current picture of RCP cannot be made mathematically precise and support this conclusion via a molecular dynamics study of hard spheres using the Lubachevsky-Stillinger compression algorithm. We suggest that this impasse can be broken by introducing the new concept of a maximally random jammed state, which can be made precise.
The wall shear rate distribution P(gamma) is investigated for pressure-driven Stokes flow through random arrangements of spheres at packing fractions 0.1 <= phi <= 0.64. For dense packings, P(gamma) is monotonic and approximately exponential. As phi --> 0.1, P(gamma) picks up additional structure which corresponds to the flow around isolated spheres, for which an exact result can be obtained. A simple expression for the mean wall shear rate is presented, based on a force-balance argument.
We extend our theory of amorphous packings of hard spheres to binary mixtures and more generally to multicomponent systems. The theory is based on the assumption that amorphous packings produced by typical experimental or numerical protocols can be identified with the infinite pressure limit of long lived metastable glassy states. We test this assumption against numerical and experimental data and show that the theory correctly reproduces the variation with mixture composition of structural observables, such as the total packing fraction and the partial coordination numbers.
The sphere packing problem is an old puzzle. We consider packings with m spheres in the unit cell (m-periodic packings). For the case m = 1 (lattice packings), Voronoi proved there are finitely many inequivalent local optima and presented an algorithm to enumerate them, and this computation has been implemented in up to d = 8 dimensions. We generalize Voronoi's method to m > 1 and present a procedure to enumerate all locally optimal 2-periodic sphere packings in any dimension, provided there are finitely many. We implement this computation in d = 3, 4, and 5 and show that no 2-periodic packing…
In the first paper of this series, we introduced Voronoi correlation functions to characterize the structure of maximally random jammed (MRJ) sphere packings across length scales. In the present paper, we determine a variety of correlation functions that can be rigorously related to effective physical properties of MRJ sphere packings and compare them to the corresponding statistical descriptors for overlapping spheres and equilibrium hard-sphere systems. Such structural descriptors arise in rigorous bounds and formulas for effective transport properties, diffusion and reactions constants, ela…
We have discovered a new family of three-dimensional crystal sphere packings that are strictly jammed (i.e., mechanically stable) and yet possess an anomalously low density. This family constitutes an uncountably infinite number of crystal packings that are subpackings of the densest crystal packings and are characterized by a high concentration of self-avoiding "tunnels" (chains of vacancies) that permeate the structures. The fundamental geometric characteristics of these tunneled crystals command interest in their own right and are described here in some detail. These include the lattice vec…
Disordered jammed packings under confinement have received considerably less attention than their \textit{bulk} counterparts and yet arise in a variety of practical situations. In this work, we study binary sphere packings that are confined between two parallel hard planes, and generalize the Torquato-Jiao (TJ) sequential linear programming algorithm [Phys. Rev. E {\bf 82}, 061302 (2010)] to obtain putative maximally random jammed (MRJ) packings that are exactly isostatic with high fidelity over a large range of plane separation distances $H$, small to large sphere radius ratio $α$ and small s…
Using sedimentation to obtain precisely controlled packings of noncohesive spheres, we find that the volume fraction $ϕ_{\rm RLP}$ of the loosest mechanically stable packing is in an operational sense well defined by a limit process. This random loose packing volume fraction decreases with decreasing pressure $p$ and increasing interparticle friction coefficient $μ$. Using X-ray tomography to correct for a container boundary effect that depends on particle size, we find for rough particles in the limit $p \to 0$ a new lower bound, $ϕ_{\rm RLP} = 0.550 \pm 0.001$.
We show for the first time that collectively jammed disordered packings of three-dimensional monodisperse frictionless hard spheres can be produced and tuned using a novel numerical protocol with packing density $ϕ$ as low as 0.6. This is well below the value of 0.64 associated with the maximally random jammed state and entirely unrelated to the ill-defined ``random loose packing'' state density. Specifically, collectively jammed packings are generated with a very narrow distribution centered at any density $ϕ$ over a wide density range $ϕ\in [0.6,~0.74048\ldots]$ with variable disorder. Our r…
Elementary smooth functions (beyond contact) are employed to construct pair correlation functions that mimic jammed disordered sphere packings. Using the g2-invariant optimization method of Torquato and Stillinger [J. Phys. Chem. B 106, 8354, 2002], parameters in these functions are optimized under necessary realizability conditions to maximize the packing fraction phi and average number of contacts per sphere Z. A pair correlation function that incorporates the salient features of a disordered packing and that is smooth beyond contact is shown to permit a phi of 0.6850: this value represents …
We introduce a generalization of the well-known random sequential addition (RSA) process for hard spheres in $d$-dimensional Euclidean space $\mathbb{R}^d$. We show that all of the $n$-particle correlation functions of this nonequilibrium model, in a certain limit called the "ghost" RSA packing, can be obtained analytically for all allowable densities and in any dimension. This represents the first exactly solvable disordered sphere-packing model in arbitrary dimension. The fact that the maximal density $ϕ(\infty)=1/2^d$ of the ghost RSA packing implies that there may be disordered sphere pack…
We study, via the replica method of disordered systems, the packing problem of hard-spheres with a square-well attractive potential when the space dimensionality, d, becomes infinitely large. The phase diagram of the system exhibits reentrancy of the liquid-glass transition line, two distinct glass states and a glass-to-glass transition, much similar to what has been previously obtained by Mode-Coupling Theory, numerical simulations and experiments. The presence of the phase reentrance implies that for a suitable choice of the intensity and attraction range, high-density sphere packings more c…
The densest local packings of N three-dimensional identical nonoverlapping spheres within a radius Rmin(N) of a fixed central sphere of the same size are obtained for selected values of N up to N = 1054. In the predecessor to this paper [A.B. Hopkins, F.H. Stillinger and S. Torquato, Phys. Rev. E 81 041305 (2010)], we described our method for finding the putative densest packings of N spheres in d-dimensional Euclidean space Rd and presented those packings in R2 for values of N up to N = 348. We analyze the properties and characteristics of the densest local packings in R3 and employ knowledge…
We characterize the structure of maximally random jammed (MRJ) sphere packings by computing the Minkowski functionals (volume, surface area, and integrated mean curvature) of their associated Voronoi cells. The probability distribution functions of these functionals of Voronoi cells in MRJ sphere packings are qualitatively similar to those of an equilibrium hard-sphere liquid and partly even to the uncorrelated Poisson point process, implying that such local statistics are relatively structurally insensitive. This is not surprising because the Minkowski functionals of a single Voronoi cell inc…
Finding the densest sphere packing in $d$-dimensional Euclidean space $\mathbb{R}^d$ is an outstanding fundamental problem with relevance in many fields, including the ground states of molecular systems, colloidal crystal structures, coding theory, discrete geometry, number theory, and biological systems. Numerically generating the densest sphere packings becomes very challenging in high dimensions due to an exponentially increasing number of possible sphere contacts and sphere configurations, even for the restricted problem of finding the densest lattice sphere packings. In this paper, we app…
Glass transition and random packing in the hard sphere system have attracted great attention due to the important role of the system in the investigation of diverse real systems including liquids, colloidal dispersions, supercooled liquids, glasses and granular materials (1-12) Despite the importance and simplicity of the system, some fundamental questions, such as the existence of an ideal glass transition (5-16), the nature of the glass transition and random packing (or jamming), and the entropy crisis or Kauzmann paradox (17,18), remain open. Based on a very accurate equation of state over …
In the first two papers of this series, we characterized the structure of maximally random jammed (MRJ) sphere packings across length scales by computing a variety of different correlation functions, spectral functions, hole probabilities, and local density fluctuations. From the remarkable structural features of the MRJ packings, especially its disordered hyperuniformity, exceptional physical properties can be expected. Here, we employ these structural descriptors to estimate effective transport and electromagnetic properties via rigorous bounds, exact expansions, and accurate analytical appr…
The densest local packing (DLP) problem in d-dimensional Euclidean space Rd involves the placement of N nonoverlapping spheres of unit diameter near an additional fixed unit-diameter sphere such that the greatest distance from the center of the fixed sphere to the centers of any of the N surrounding spheres is minimized. Solutions to the DLP problem are relevant to the realizability of pair correlation functions for packings of nonoverlapping spheres and might prove useful in improving upon the best known upper bounds on the maximum packing fraction of sphere packings in dimensions greater tha…
Packing spheres efficiently in large dimension $d$ is a particularly difficult optimization problem. In this paper we add an isotropic interaction potential to the pure hard-core repulsion, and show that one can tune it in order to maximize a lower bound on packing density. Our results suggest that exponentially many (in the number of particles) distinct disordered sphere packings can be effectively constructed by this method, up to a packing fraction close to $7\, d\, 2^{-d}$. The latter is determined by solving the inverse problem of maximizing the dynamical glass transition over the space o…
The densest local packings of N identical nonoverlapping spheres within a radius Rmin(N) of a fixed central sphere of the same size are obtained using a nonlinear programming method operating in conjunction with a stochastic search of configuration space. Knowledge of Rmin(N) in d-dimensional Euclidean space allows for the construction both of a realizability condition for pair correlation functions of sphere packings and an upper bound on the maximal density of infinite sphere packings. In this paper, we focus on the two-dimensional circular disk problem. We find and present the putative dens…
The most efficient way to pack equally sized spheres isotropically in 3D is known as the random close packed state, which provides a starting point for many approximations in physics and engineering. However, the particle size distribution of a real granular material is never monodisperse. Here we present a simple but accurate approximation for the random close packing density of hard spheres of any size distribution, based upon a mapping onto a one-dimensional problem. To test this theory we performed extensive simulations for mixtures of elastic spheres with hydrodynamic friction. The simula…
We apply a recent one-dimensional algorithm for predicting random close packing fractions of polydisperse hard spheres [Farr and Groot, J. Chem. Phys. 133, 244104 (2009)] to the case of lognormal distributions of sphere sizes and mixtures of such populations. We show that the results compare well to two much slower algorithms for directly simulating spheres in three dimensions, and show that the algorithm is fast enough to tackle inverse problems in particle packing: designing size distributions to meet required criteria. The one-dimensional method used in this paper is implemented as a comput…
We numerically produce fully amorphous assemblies of frictionless spheres in three dimensions and study the jamming transition these packings undergo at large volume fractions. We specify four protocols yielding a critical value for the jamming volume fraction which is sharply defined in the limit of large system size, but is different for each protocol. Thus, we directly establish the existence of a continuous range of volume fraction where nonequilibrium jamming transitions occur. However, these jamming transitions share the same critical behaviour. Our results suggest that, even in the abse…
We study theoretically and numerically the microscopic cause of the mechanical stability of hard sphere glasses near their maximum packing. We show that, after coarse-graining over time, the hard sphere interaction can be described by an effective potential which is exactly logarithmic at the random close packing $ϕ_c$. This allows to define normal modes, and to apply recent results valid for elastic networks: mechanical stability is a non-local property of the packing geometry, and is characterized by some length scale $l^*$ which diverges at $ϕ_c$ [1, 2]. We compute the scaling of the bulk a…
We have formulated the problem of generating periodic dense paritcle packings as an optimization problem called the Adaptive Shrinking Cell (ASC) formulation [S. Torquato and Y. Jiao, Phys. Rev. E {\bf 80}, 041104 (2009)]. Because the objective function and impenetrability constraints can be exactly linearized for sphere packings with a size distribution in $d$-dimensional Euclidean space $\mathbb{R}^d$, it is most suitable and natural to solve the corresponding ASC optimization problem using sequential linear programming (SLP) techniques. We implement an SLP solution to produce robustly a wid…
We present an efficient Monte Carlo method for the lattice sphere packing problem in d dimensions. We use this method to numerically discover de novo the densest lattice sphere packing in dimensions 9 through 20. Our method goes beyond previous methods not only in exploring higher dimensions but also in shedding light on the statistical mechanics underlying the problem in question. We observe evidence of a phase transition in the thermodynamic limit $d\to\infty$. In the dimensions explored in the present work, the results are consistent with a first-order crystallization transition, but leave …
The densest binary sphere packings in the alpha-x plane of small to large sphere radius ratio alpha and small sphere relative concentration x have historically been very difficult to determine. Previous research had led to the prediction that these packings were composed of a few known "alloy" phases including, for example, the AlB2 (hexagonal omega), HgBr2, and AuTe2 structures, and to XYn structures composed of close-packed large spheres with small spheres (in a number ratio of n to 1) in the interstices, e.g., the NaCl packing for n = 1. However, utilizing an implementation of the Torquato-…
We show that hard spheres confined between two parallel hard plates pack denser with periodic adaptive prismatic structures which are composed of alternating prisms of spheres. The internal structure of the prisms adapts to the slit height which results in close packings for a range of plate separations, just above the distance where three intersecting square layers fit exactly between the plates. The adaptive prism phases are also observed in real-space experiments on confined sterically stabilized colloids and in Monte Carlo simulations at finite pressure.
We generate and study an ensemble of isostatic jammed hard-sphere lattices. These lattices are obtained by compression of a periodic system with an adaptive unit cell containing a single sphere until the point of mechanical stability. We present detailed numerical data about the densities, pair correlations, force distributions, and structure factors of such lattices. We show that this model retains many of the crucial structural features of the classical hard-sphere model and propose it as a model for the jamming and glass transitions that enables exploration of much higher dimensions than ar…
We present a statistical mechanical description of randomly packed spherical particles, where the average coordination number is treated as a macroscopic thermodynamic variable. The overall packing entropy is shown to have two contributions: geometric, reflecting statistical weights of individual configurations, and topological, which corresponds to the number of topologically distinct states. Both of them are computed in the thermodynamic limit for isostatic packings in 2D and 3D, and the result is further expanded to the case of "floppy" particle clusters. The theory is directly applicable t…
The question of whether the known virial coefficients are enough to determine the packing fraction $η_\infty$ at which the fluid equation of state of a hard-sphere fluid diverges is addressed. It is found that the information derived from the direct Padé approximants to the compressibility factor constructed with the virial coefficients is inconclusive. An alternative approach is proposed which makes use of the same virial coefficients and of the equation of state in a form where the packing fraction is explicitly given as a function of the pressure. The results of this approach both for hard-…
Using computed x-ray tomography we determine the three dimensional (3d) structure of binary hard sphere mixtures as a function of composition and size ratio of the particles, q. Using a recently introduced four-point correlation function we reveal that this 3d structure has on intermediate and large length scales a surprisingly regular order, the symmetry of which depends on q. The related structural correlation length has a minimum at the composition at which the packing fraction is highest. At this composition also the number of different local particle arrangements has a maximum, indicating…
In a recent paper (cond-mat/0506445) we derived an expression for the replicated free energy of a liquid of hard spheres based on the HNC free energy functional. An approximate equation of state for the glass and an estimate of the random close packing density were obtained in d=3. Here we show that the HNC approximation is not needed: the same expression can be obtained from the full diagrammatic expansion of the replicated free energy. Then, we consider the asymptotics of this expression when the space dimension d is very large. In this limit, the entropy of the hard sphere liquid has been c…
Glass transition is accompanied by a rapid growth of the structural relaxation time and a concomitant decrease of configurational entropy. It remains unclear whether the transition has a thermodynamic origin, and whether the dynamic arrest is associated with the growth of a certain static order. Using granular packing as a model hard-sphere glass, we show the glass transition as a thermodynamic phase transition with a "hidden" polytetrahedral order. This polytetrahedral order is spatially correlated with the slow dynamics. It is geometrically frustrated and has a peculiar fractal dimension. Ad…
High strength-to-weight ratio materials can be constructed by either maximizing strength or minimizing weight. Tensegrity structures and aerogels take very different paths to achieving high strength-to-weight ratios but both rely on internal tensile forces. In the absence of tensile forces, removing material eventually destabilizes a structure. Attempts to maximize the strength-to-weight ratio with purely repulsive spheres have proceeded by removing spheres from already stable crystalline structures. This results in a modestly low density and a strength-to-weight ratio much worse than can be a…
