Wide Range Of Packing Fractions Research Articles

The interplay between chemo-phoretic interactions and crowding in active colloids.

Many motile microorganisms communicate with each other and their environments via chemical signaling which leads to long-range interactions mediated by self-generated chemical gradients. However, consequences of the interplay between crowding and chemotactic interactions on their collective behavior remain poorly understood. In this work, we use Brownian dynamics simulations to investigate the effect of packing fraction on the formation of non-equilibrium structures in a monolayer of diffusiophoretic self-propelled colloids as a model for chemically active particles. Focusing on the case when a chemical field induces attractive positional and repulsive orientational interactions, we explore dynamical steady-states of active colloids of varying packing fractions and degrees of motility. In addition to collapsed, active gas, and dynamical clustering steady-states reported earlier for low packing fractions, a new phase-separated state emerges. The phase separation results from a competition between long-range diffusiophoretic interactions and motility and is observed at moderate activities and a wide range of packing fractions. Our analysis suggests that the fraction of particles in the largest cluster is a suitable order parameter for capturing the transition from an active gas and dynamical clustering states to a phase-separated state.

Kinetic Frustration Effects on Dense Two-Dimensional Packings of Convex Particles and Their Structural Characteristics.

The study of hard-particle packings is of fundamental importance in physics, chemistry, cell biology, and discrete geometry. Much of the previous work on hard-particle packings concerns their densest possible arrangements. By contrast, we examine kinetic effects inevitably present in both numerical and experimental packing protocols. Specifically, we determine how changing the compression/shear rate of a two-dimensional packing of noncircular particles causes it to deviate from its densest possible configuration, which is always periodic. The adaptive shrinking cell (ASC) optimization scheme maximizes the packing fraction of a hard-particle packing by first applying random translations and rotations to the particles and then isotropically compressing and shearing the simulation box repeatedly until a possibly jammed state is reached. We use a stochastic implementation of the ASC optimization scheme to mimic different effective time scales by varying the number of particle moves between compressions/shears. We generate dense, effectively jammed, monodisperse, two-dimensional packings of obtuse scalene triangle, rhombus, curved triangle, lens, and "ice cream cone" (a semicircle grafted onto an isosceles triangle) shaped particles, with a wide range of packing fractions and degrees of order. To quantify these kinetic effects, we introduce the kinetic frustration index K, which measures the deviation of a packing from its maximum possible packing fraction. To investigate how kinetics affect short- and long-range ordering in these packings, we compute their spectral densities χ̃V(k) and characterize their contact networks. We find that kinetic effects are most significant when the particles have greater asphericity, less curvature, and less rotational symmetry. This work may be relevant to the design of laboratory packing protocols.

Athermal rheology of weakly attractive soft particles.

We study the rheology of a soft particulate system where the interparticle interactions are weakly attractive. Using extensive molecular dynamics simulations, we scan across a wide range of packing fractions (ϕ), attraction strengths (u), and imposed shear rates (γ[over ̇]). In striking contrast to repulsive systems, we find that at small shear rates generically a fragile isostatic solid is formed even if we go to ϕ≪ϕ_{J}. Further, with increasing shear rates, even at these low ϕ, nonmonotonic flow curves occur which lead to the formation of persistent shear bands in large enough systems. By tuning the damping parameter, we also show that inertia plays an important role in this process. Furthermore, we observe enhanced particle dynamics in the attraction-dominated regime as well as a pronounced anisotropy of velocity and diffusion constant, which we take as precursors to the formation of shear bands. At low enough ϕ, we also observe structural changes via the interplay of low shear rates and attraction with the formation of microclusters and voids. Finally, we characterize the properties of the emergent shear bands, and thereby, we find surprisingly small mobility of these bands, leading to prohibitively long time scales and extensive history effects in ramping experiments.

Assessment of the micro-structure and depletion potentials in two-dimensional binary mixtures of additive hard-disks.

Depletion forces are a particular class of effective interactions that have been mainly investigated in binary mixtures of hard-spheres in bulk. Although there are a few contributions that point toward the effects of confinement on the depletion potential, little is known about such entropic potentials in two-dimensional colloidal systems. From theoretical point of view, the problem resides in the fact that there is no general formulation of depletion forces in arbitrary dimensions and, typically, any approach that works well in three dimensions has to be reformulated for lower dimensionality. However, we have proposed a theoretical framework, based on the formalism of contraction of the description within the integral equations theory of simple liquids, to account for effective interactions in colloidal liquids, whose main feature is that it does not need to be readapted to the problem under consideration. We have also shown that such an approach allows one to determine the depletion pair potential in three-dimensional colloidal mixtures even near to the demixing transition, provided the bridge functions are sufficiently accurate to correctly describe the spatial correlation between colloids [E. López-Sánchez et al., J. Chem. Phys. 139, 104908 (2013)]. We here report an extensive analysis of the structure and the entropic potentials in binary mixtures of additive hard-disks. In particular, we show that the same functional form of the modified-Verlet closure relation used in three dimensions can be straightforwardly employed to obtain an accurate solution for two-dimensional colloidal mixtures in a wide range of packing fractions, molar fractions, and size asymmetries. Our theoretical results are explicitly compared with the ones obtained by means of event-driven molecular dynamics simulations and recent experimental results. Furthermore, to assess the accuracy of our predictions, the depletion potentials are used in an effective one-component model to reproduce the structure of either the big or the small disks. This demonstrates the robustness of our theoretical scheme even in two dimensions.

Effective potentials in a bidimensional vibrated granular gas.

We present a numerical study of the spatial correlations of a quasi-two-dimensional granular fluid kept in a nonstatic steady state via vertical shaking. The simulations explore a wide range of vertical accelerations, restitution coefficients, and packing fractions, always staying below the crystallization limit. From the simulations we obtain the relevant pair distribution functions (PDFs), and effective potentials for the interparticle interaction are extracted from these PDFs via the Ornstein-Zernike equation with the Percus-Yevick closure. The correlations in the granular structures originating from these effective potentials are checked against the originating PDF using standard Monte Carlo simulations, and we find in general an excellent agreement. The resulting effective potentials show an increase of the spatial correlation at contact with the decreasing values of the restitution coefficient, and a tendency of the potentials to display deeper wells for more dissipative dynamics. A general exception to this trend appears for a range of values of the forcing, which depends on the restitution coefficient, but not on the density, where resonant bouncing increases correlations, resulting in deeper potential wells. The nature of these resonances is explored and shown to be the result of synchronization in the parabolic flights of the particles.

Hysteresis, reentrance, and glassy dynamics in systems of self-propelled rods.

Nonequilibrium active matter made up of self-driven particles with short-range repulsive interactions is a useful minimal system to study active matter as the system exhibits collective motion and nonequilibrium order-disorder transitions. We studied high-aspect-ratio self-propelled rods over a wide range of packing fractions and driving to determine the nonequilibrium state diagram and dynamic properties. Flocking and nematic-laning states occupy much of the parameter space. In the flocking state, the average internal pressure is high and structural and mechanical relaxation times are long, suggesting that rods in flocks are in a translating glassy state despite overall flock motion. In contrast, the nematic-laning state shows fluidlike behavior. The flocking state occupies regions of the state diagram at both low and high packing fraction separated by nematic-laning at low driving and a history-dependent region at higher driving; the nematic-laning state transitions to the flocking state for both compression and expansion. We propose that the laning-flocking transitions are a type of glass transition that, in contrast to other glass-forming systems, can show fluidization as density increases. The fluid internal dynamics and ballistic transport of the nematic-laning state may promote collective dynamics of rod-shaped micro-organisms.

Structural properties of dense hard sphere packings.

We numerically study structural properties of mechanically stable packings of hard spheres (HS), in a wide range of packing fractions 0.53 ≤ ϕ ≤ 0.72. Detailed structural information is obtained from the analysis of orientational order parameters, which clearly reveals a disorder-order phase transition at the random close packing (RCP) density, ϕc ≃ 0.64. Above ϕc, the crystalline nuclei form 3D-like clusters, which upon further desification transform into alternating planar-like layers. We also find that particles with icosahedral symmetry survive only in a narrow density range in the vicinity of the RCP transition.

Compressive consolidation of strongly aggregated particle gels

The compressive yield stress of particle gels shows a highly nonlinear dependence on the packing fraction. We have studied continuous compression processes, and discussed the packing fraction dependence with the particle scale rearrangements. The 2D simulation of uniaxial compression was applied to fractal networks, and the required compressive stresses were evaluated for a wide range of packing fractions that approached close packing. The compression acts to reduce the size of the characteristic structural entities (i.e. the correlation length of the structure). We observed three stages of compression: (I) elastic-dominant regime; (II) single-mode plastic regime, where the network strengths are determined by the typical length scale and the rolling mode; and (III) multi-mode plastic regime, where sliding mode and connection breaks are important. We also investigated the way of losing the fractal correlation under compression. It turns out that both fractal dimension $D_{\mathrm{f}}$ and correlation length $\xi$ start to change from the early stage of compression, which is different from the usual assumption in theoretical models.

Ratio of effective temperature to pressure controls the mobility of sheared hard spheres

Using molecular dynamics simulations, we calculate fluctuations and responses for steadily sheared hard spheres over a wide range of packing fractions φ and shear strain rates γ[over ̇], using two different methods to dissipate energy. To a good approximation, shear stress and density fluctuations are related to their associated response functions by a single effective temperature T(eff) that is equal to or larger than the kinetic temperature T(kin). We find a crossover in the relationship between the relaxation time τ and the the nondimensionalized effective temperature T(eff)/pσ(3), where p is the pressure and σ is the sphere diameter. In the solid response regime, the behavior at a fixed packing fraction satisfies τ ̇γ∝exp(-cpσ(3)/T(eff)), where c depends weakly on φ, suggesting that the average local yield strain is controlled by the effective temperature in a way that is consistent with shear transformation zone theory. In the fluid response regime, the relaxation time depends on T(eff)/pσ(3) as it depends on T(kin)/pσ(3) in equilibrium. This regime includes both near-equilibrium conditions where T(eff)≃T(kin) and far-from-equilibrium conditions where T(eff)≠T(kin). We discuss the implications of our results for systems with soft repulsive interactions.

Shear thickening and jamming in densely packed suspensions of different particle shapes

We investigated the effects of particle shape on shear thickening in densely packed suspensions. Rods of different aspect ratios and nonconvex hooked rods were fabricated. Viscosity curves and normal stresses were measured using a rheometer for a wide range of packing fractions for each shape. Suspensions of each shape exhibit qualitatively similar discontinuous shear thickening. The logarithmic slope of the stress vs shear rate increases dramatically with packing fraction and diverges at a critical packing fraction φ(c) which depends on particle shape. The packing fraction dependence of the viscosity curves for different convex shapes can be collapsed when the packing fraction is normalized by φ(c). Intriguingly, viscosity curves for nonconvex particles do not collapse on the same set as convex particles, showing strong shear thickening over a wider range of packing fraction. The value of φ(c) is found to coincide with the onset of a yield stress at the jamming transition, suggesting the jamming transition also controls shear thickening. The yield stress is found to correspond with trapped air in the suspensions, and the scale of the stress can be attributed to interfacial tension forces which dramatically increase above φ(c) due to the geometric constraints of jamming. Using this connection we show that the jamming transition can be identified by simply looking at the surface of suspensions. The relationship between shear and normal stresses is found to be linear in both the shear thickening and jammed regimes, indicating that the shear stresses come from friction. In the limit of zero shear rate, normal stresses pull the rheometer plates together due to the surface tension of the liquid below φ(c), but push the rheometer plates apart due to jamming above φ(c).

Hard sphere fluids at a soft repulsive wall: A comparative study using Monte Carlo and density functional methods

Hard-sphere fluids confined between parallel plates at a distance D apart are studied for a wide range of packing fractions including also the onset of crystallization, applying Monte Carlo simulation techniques and density functional theory. The walls repel the hard spheres (of diameter σ) with a Weeks-Chandler-Andersen (WCA) potential V(WCA)(z) = 4ε[(σ(w)/z)(12) - (σ(w)/z)(6) + 1/4], with range σ(w) = σ/2. We vary the strength ε over a wide range and the case of simple hard walls is also treated for comparison. By the variation of ε one can change both the surface excess packing fraction and the wall-fluid (γ(wf)) and wall-crystal (γ(wc)) surface free energies. Several different methods to extract γ(wf) and γ(wc) from Monte Carlo (MC) simulations are implemented, and their accuracy and efficiency is comparatively discussed. The density functional theory (DFT) using fundamental measure functionals is found to be quantitatively accurate over a wide range of packing fractions; small deviations between DFT and MC near the fluid to crystal transition need to be studied further. Our results on density profiles near soft walls could be useful to interpret corresponding experiments with suitable colloidal dispersions.

Density Profile of a Hard Disk Liquid System under Gravity

The free energy and the density profile of a hard disk liquid system under gravity are calculated by using the dimensional crossover of Rosenfeld hard sphere (3D) functional as well as the functional constructed from the scaled-particle theory which is considered to be very accurate. The two methods give the consistent results for a wide range of packing fractions.

Diversity of order and densities in jammed hard-particle packings.

Recently the conventional notion of random close packing has been supplanted by the more appropriate concept of the maximally random jammed (MRJ) state. This inevitably leads to the necessity of distinguishing the MRJ state among the entire collection of jammed packings. While the ideal method of addressing this question would be to enumerate and classify all possible jammed hard-sphere configurations, practical limitations prevent such a method from being employed. Instead, we generate numerically a large number of representative jammed hard-sphere configurations (primarily relying on a slight modification of the Lubachevsky-Stillinger algorithm to do so) and evaluate several commonly employed order metrics for each of these packings. Our investigation shows that, even in the large-system limit, jammed systems of hard spheres can be generated with a wide range of packing fractions from phi approximately 0.52 to the fcc limit (phi approximately 0.74). Moreover, at a fixed packing fraction, the variation in the order can be substantial, indicating that the density alone does not uniquely characterize a packing. Interestingly, each order metric evaluated yielded a relatively consistent estimate for the packing fraction of the maximally random jammed state (phi(MRJ) approximately 0.63). This estimate, however, is compromised by the weaknesses in the order metrics available, and we propose several guiding principles for future efforts to define more broadly applicable metrics.

Equation of state of the hard-sphere solid: The modified weighted-density approximation with a static solid reference state

We have investigated the high-density hard-sphere solid through density-functional theory by applying our recent formulation of the modified weighted-density approximation (MWDA) with a static solid reference state. Our model utilizes both information about the fluid state, modeled by the Percus-Yevick approximation, as well as physical insight into the static solid. We find very good agreement with computer simulation data for the equation of state, as well as for the ideal and excess components of the pressure, and are able to improve the results from the original MWDA model over a wide range of packing fractions. The degree of particle localization and the value of the Lindemann parameter for the high-density hard-sphere solid are also improved over the original MWDA theory. Finally, we comment on the result that the excess pressure is negative for most packing fractions, suggesting possible physical means for this observation.

Equation of state of polymer melts: Numerical results for athermal freely jointed chain fluids

Our microscopic RISM integral equation theory for the virial equation of state of polymer liquids developed in the preceding paper is numerically implemented for athermal melts composed of freely-jointed chains interacting via hard core site–site potentials. A modified ideal description of the single chain intramolecular correlations is employed which rigorously enforces the nonoverlapping core condition and leads to significant local coil expansion. Comparison of the theoretically computed virial pressure for tangent diatomics and short chains with available Monte Carlo simulation results over a wide range of packing fractions suggests the theory is quite accurate. Significant inconsistencies between the pressure computed via the virial and compressibility routes are found and discussed in light of the known limitations of the RISM method and the importance of self-consistency corrections for flexible chain molecule liquids. A detailed numerical study of the density and degree of polymerization dependences of the total virial pressure, and its individual two- and three-body components, is presented, along with the limiting infinite chain behavior. The integral equation results are also compared with the predictions of several simple mean field and/or lattice models for both short chains and high polymers. Significant, and in some cases massive, differences are found between the predictions of the various approaches and the integral equation calculations which are attributed to the neglect of polymeric connectivity, intermolecular correlations, and/or the use of a lattice model inherent to the simple theories. In particular, both the density dependence of the pressure and its sensitivity to degree of polymerization are found to be much stronger than the simple theories predict due to self-screening and correlation hole effects absent in the latter. Finally, model calculations of the intermolecular radial distribution function and static structure factor at fixed pressure are performed for several degrees of polymerization and are found to be very weakly dependent on chain length due to compensating effects associated with a molecular weight dependent packing fraction.