Hard-disk Fluid Research Articles

Colloids get hardcore: New simulation technique yields thermodynamic theory of hard-disk fluids

Coupling Gibbs-Cahn integration with Monte Carlo simulations yields accurately modeled solid-liquid interfacial properties of a 2-D system.

Direct Liquid to Crystal Transition in a Quasi-Two-Dimensional Colloidal Membrane

Using synchrotron-based small-angle X-ray scattering, we study rigid fd viruses assembled into isolated monolayers from mixtures with a nonabsorbing polymer, which acts as an osmotic agent. As the polymer concentration increases, we observe a direct liquid to crystal transition, without an intermediate hexatic phase, in contrast with many other similar systems, such as concentrated DNA phases or packings of surfactant micelles. We tentatively attribute this effect to the difference in stiffness. The liquid phase can be well described by a hard-disk fluid, while we model the crystalline one as a hexagonal harmonic lattice and we evaluate its elastic constants.

Equation of state of polydisperse hard-disk mixtures in the high-density regime.

A proposal to link the equation of state of a monocomponent hard-disk fluid to the equation of state of a polydisperse hard-disk mixture is presented. Event-driven molecular dynamics simulations are performed to obtain data for the compressibility factor of the monocomponent fluid and of 26 polydisperse mixtures with different size distributions. Those data are used to assess the proposal and to infer the values of the compressibility factor of the monocomponent hard-disk fluid in the metastable region from those of mixtures in the high-density region. The collapse of the curves for the different mixtures is excellent in the stable region. In the metastable regime, except for two mixtures in which crystallization is present, the outcome of the approach exhibits a rather good performance. The simulation results indicate that a (reduced) variance of the size distribution larger than about 0.01 is sufficient to avoid crystallization and explore the metastable fluid branch.

Effect of crowding and confinement on first-passage times: A model study.

We study the "color dynamics" of a hard-disk fluid confined in an annulus, as well as the corresponding hard-sphere system in three dimensions, using event-driven simulation in order to explore the effect of confinement and self-crowding on the search for targets. We compute the mean first-passage times (MFPTs) of red particles transiting from the outer to the inner boundary as well as those of blue particles passing from the inner to the outer boundary for different packing fractions and geometries. In the steady state the reaction rate, defined as the rate of collision of red particles with the inner boundary, is inversely proportional to the sum of the MFPTs. The reaction rate is wall mediated (ballistic) at low densities and diffusion controlled at higher densities and displays a maximum at intermediate densities. At moderate to high densities, the presence of layering has a strong influence on the search process. The numerical results for the reaction rate and MFPTs are compared with a ballistic model at low densities and a Smoluchowski approach with uniform diffusivities at higher densities. We discuss the reasons for the limited validity of the theoretical approaches. The maximum in the reaction rate is qualitatively well rendered by a Bosanquet-like approach that interpolates between the two regimes. Finally, we compute the position-dependent diffusivity from the MFPTs and observe that it is out of phase with the radial density.

Frustration of freezing in a two dimensional hard-core fluid due to particle shape anisotropy

The freezing mechanism suggested for a fluid composed of hard disks [Huerta et al., Phys. Rev. E, 2006, 74, 061106] is used here to probe the fluid-to-solid transition in a hard-dumbbell fluid composed of overlapping hard disks with a variable length between disk centers. Analyzing the trends in the shape of second maximum of the radial distribution function of the planar hard-dumbbell fluid it has been found that the type of transition could be sensitive to the length of hard-dumbbell molecules. From the ${NpT}$ Monte Carlo simulations data we show that if a hard-dumbbell length does not exceed 15% of the disk diameter, the fluid-to-solid transition scenario follows the case of a hard-disk fluid, i.e., the isotropic hard-dumbbell fluid experiences freezing. However, for a hard-dumbbell length larger than 15% of disk diameter, there is evidence that fluid-to-solid transition may change to continuous transition, i.e., such an isotropic hard-dumbbell fluid will avoid freezing.

Glasslike behavior of a hard-disk fluid confined to a narrow channel.

Disks moving in a narrow channel have many features in common with the glassy behavior of hard spheres in three dimensions. In this paper we study the caging behavior of the disks that sets in at characteristic packing fraction ϕ(d). Four-point overlap functions similar to those studied when investigating dynamical heterogeneities have been determined from event-driven molecular dynamics simulations and the time-dependent dynamical length scale has been extracted from them. The dynamical length scale increases with time and, on the equilibration time scale, it is proportional to the static length scale associated with the zigzag ordering in the system, which grows rapidly above ϕ(d). The structural features responsible for the onset of caging and the glassy behavior are easy to identify as they show up in the structure factor, which we have determined exactly from the transfer-matrix approach.

Monte Carlo simulations of the two-dimensional dipolar fluid

We study a two-dimensional fluid of dipolar hard disks by Monte Carlo simulations in a square with periodic boundary conditions and on the surface of a sphere. The theory of the dielectric constant and the asymptotic behaviour of the equilibrium pair correlation function in the fluid phase are derived for both geometries. After having established the equivalence of the two methods we study the stability of the liquid phase in the canonical ensemble. We give evidence of a phase made of living polymers at low temperatures and provide a tentative phase diagram.

Scaling laws and bulk-boundary decoupling in heat flow.

When driven out of equilibrium by a temperature gradient, fluids respond by developing a nontrivial, inhomogeneous structure according to the governing macroscopic laws. Here we show that such structure obeys strikingly simple scaling laws arbitrarily far from equilibrium, provided that both macroscopic local equilibrium and Fourier's law hold. Extensive simulations of hard disk fluids confirm the scaling laws even under strong temperature gradients, implying that Fourier's law remains valid in this highly nonlinear regime, with putative corrections absorbed into a nonlinear conductivity functional. In addition, our results show that the scaling laws are robust in the presence of strong finite-size effects, hinting at a subtle bulk-boundary decoupling mechanism which enforces the macroscopic laws on the bulk of the finite-sized fluid. This allows one to measure the marginal anomaly of the heat conductivity predicted for hard disks.

Collective excitations in 2D hard-disc fluid

Collective dynamics of a two-dimensional (2D) hard-disc fluid was studied by molecular dynamics simulations in the range of packing fractions that covers states up to the freezing. Some striking features concerning collective excitations in this system were observed. In particular, the short-wavelength shear waves while being absent at low packing fractions were observed in the range of high packing fractions, just before the freezing transition in a 2D hard-disc fluid. In contrast, the so-called “positive sound dispersion” typically observed in dense Lennard-Jones-like fluids, was not detected for the 2D hard-disc fluid. The ratio of specific heats in the 2D hard-disc fluid shows a monotonic increase with density approaching the freezing, resembling in this way the similar behavior in the vicinity of the Widom line in the case of supercritical fluids.

Persistence-length renormalization of polymers in a crowded environment of hard disks.

The most conspicuous property of a semiflexible polymer is its persistence length, defined as the decay length of tangent correlations along its contour. Using an efficient stochastic growth algorithm to sample polymers embedded in a quenched hard-disk fluid, we find apparent wormlike chain statistics with a renormalized persistence length. We identify a universal form of the disorder renormalization that suggests itself as a quantitative measure of molecular crowding.

Dynamics of clustering in freely cooling granular fluid

Via the event-driven molecular-dynamics simulations, we have studied the structure and dynamics in a model granular fluid of hard discs in space dimension d = 2. Inelastic collisions among these discs lead to clustering, resembling the kinetics in a vapor-liquid phase transition. The structural growth of these clusters are quantified via an application of finite-size scaling theory. We also present results for the decay of the kinetic energy. Discussion on the validity of a scaling argument, connecting the latter with the time dependence of clustering, is provided. Further, a striking difference in the finite-size effects of the kinetics with those of the phase transition dynamics is pointed out.

Static and dynamical properties of a hard-disk fluid confined to a narrow channel.

The thermodynamic properties of disks moving in a channel sufficiently narrow that they can collide only with their nearest neighbors can be solved exactly by determining the eigenvalues and eigenfunctions of an integral equation. Using it, we have determined the correlation length ξ of this system. We have developed an approximate solution which becomes exact in the high-density limit. It describes the system in terms of defects in the regular zigzag arrangement of disks found in the high-density limit. The correlation length is then effectively the spacing between the defects. The time scales for defect creation and annihilation are determined with the help of transition-state theory, as is the diffusion coefficient of the defects, and these results are found to be in good agreement with molecular dynamics simulations. On compressing the system with the Lubachevsky-Stillinger procedure, jammed states are obtained whose packing fractions ϕJ are a function of the compression rate γ. We find a quantitative explanation of this dependence by making use of the Kibble-Zurek hypothesis. We have also determined the point-to-set length scale ξPS for this system. At a packing fraction ϕ close to its largest value ϕmax, ξPS has a simple power law divergence, ξPS∼1/(1-ϕ/ϕmax), while ξ diverges much faster, ln(ξ)∼1/(1-ϕ/ϕmax).

Dimensional crossover of hard parallel cylinders confined on cylindrical surfaces

We derive, from the dimensional-crossover criterion, a fundamental-measure density functional for parallel hard curved rectangles moving on a cylindrical surface. We derive it from the density functional of circular arcs of length σ with centers of mass located on an external circumference of radius R(0). The latter functional in turn is obtained from the corresponding two-dimensional functional for a fluid of hard disks of radius R on a flat surface with centers of mass confined onto a circumference of radius R(0). Thus the curved length of closest approach between the two centers of mass of hard disks on this circumference is σ=2R(0)sin(-1)(R/R(0)), the length of the circular arcs. From the density functional of circular arcs, and by applying a dimensional expansion procedure to the spatial dimension orthogonal to the plane of the circumference, we finally obtain the density functional of curved rectangles of edge lengths σ and L. Along with the derivation, we show that, when the centers of mass of the disks are confined to the exterior circumference of a circle of radius R(0),(i) for R(0)>R, the exact Percus one-dimensional (1D) density functional of circular arcs of length 2R(0)sin(-1)(R/R(0)) is obtained, and (ii) for R(0)<R, the zero-dimensional limit (a cavity that can hold one particle at most) is recovered. We also show that, for R(0)>R, the obtained functional is equivalent to that of parallel hard rectangles on a flat surface of the same lengths, except that now the density profile of curved rectangles is a periodic function of the azimuthal angle, ρ(φ,z)=ρ(φ+2π,z). The phase behavior of a fluid of aligned curved rectangles is obtained by calculating the free-energy branches of smectic, columnar, and crystalline phases for different values of the ratio R(0)/R in the range 1<R(0)/R≤4; the smectic phase turns out to be the most stable except for R(0)/R=4, where the crystalline phase becomes reentrant in a small range of packing fractions. When R(0)/R<1 the transition is absent, since the density functional of curved rectangles reduces to the 1D Percus functional.

Grad's moment method for a granular fluid at moderate densities: Navier-Stokes transport coefficients

The Navier-Stokes transport coefficients of a granular dense fluid of smooth inelastic hard disks or spheres are explicitly determined by solving the inelastic Enskog equation by means of Grad's moment method. The transport coefficients are explicitly determined as functions of the (constant) coefficient of restitution and the solid volume fraction. In addition, the cooling rate is also calculated to first order in the spatial gradients. The calculations are performed for an arbitrary number of dimensions. The results are not limited to small dissipation and are expected to apply at moderate densities. It is found that the expressions of the Navier-Stokes transport coefficients and the cooling rate agree with those previously obtained from the Chapman-Enskog method by using the leading terms in a Sonine polynomial expansion. This shows the equivalence between both methods for granular fluids in the Navier-Stokes approximation. A comparison with previous results derived from Grad's moment method for inelastic disks and spheres is also carried out.

Towards frustration of freezing transition in a binary hard-disk mixture

The freezing mechanism, recently suggested for a monodisperse hard-disk fluid [Huerta et al., Phys. Rev. E, 2006, 74, 061106] is extended here to an equimolar binary hard-disk mixtures. We are showing that for diameter ratios, smaller than 1.15 the global orientational order parameter of the binary mixture behaves like in the case of a monodisperse fluid. Namely, by increasing the disk number density there is a tendency to form a crystalline-like phase. However, for diameter ratios larger than 1.15 the binary mixtures behave like a disordered fluid. We use some of the structural and thermodynamic properties to compare and discuss the behavior as a function of diameter ratio and packing fraction.

Generalized bond order parameters to characterize transient crystals

Higher order parameters in the hard disk fluid are computed to investigate the number, the lifetime, and size of transient crystal nuclei in the pre-freezing phase. The methodology introduces further neighbor shells bond orientational order parameters and coarse-grains the correlation functions needed for the evaluation of the stress autocorrelation function for the viscosity. We successfully reproduce results by the previous collision method for the pair orientational correlation function, but some two orders of magnitude faster. This speed-up allows calculating the time dependent four body orientational correlation between two different pairs of particles as a function of their separation, needed to characterize the size of the transient crystals. The result is that the slow decay of the stress autocorrelation function near freezing is due to a large number of rather small crystal nuclei lasting long enough to lead to the molasses tail.

Microrheological consequences of attractive colloid-colloid potentials in a two-dimensional Brownian fluid

By using microrheological methods commonly employed in videomicroscopy experiments, we study the rheology of a two-dimensional computational fluid formed by Brownian disks with the aim of exploring the influence of some effective colloid-colloid attractive interactions. The model of fluid is developed by Brownian dynamics simulations without hydrodynamical interactions, and it is characterized by calculating its equation of state from the pair distribution function. Micromechanical properties, relative and intrinsic viscosity and freezing are discussed. Then, we include attractive forces such a Asakura-Oosawa depletion force or an empiric expression proposed by Grier and Hal (GH) for an anomalous electrostatic potential observed in confined and charged colloids. By using both potentials, viscosity is clearly increased, but when the GH potential is included, viscoelastic gel state is reached for intermediate values of surface concentration. Finally, we analyse the influence of the attractive potentials in the breaking-up by thermal fluctuations of linear chains formed by 2D particles, finding that the GH potential reduces the characteristical time at which the disks can be considered as disaggregated. In this work, we employ an experimental-like methodology for the study of a Brownian hard-disk fluid, providing a very useful link with experimental procedures.

An analytic solution for the magnetization of two-dimensional ferrofluids based on the mean spherical approximation

An analytic formula is derived for the magnetization of a two-dimensional dipolar hard disk fluid using a variational functional series expansion of the free energy as a function of the orientational distribution function. The excess term expressing the effect of the intermolecular forces is calculated on the basis of the mean spherical approximation. Comparison with our own Monte Carlo simulation data shows excellent agreement for large external fields and for the zero-field susceptibility. At intermediate field strengths, the agreement is satisfactory for moderate dipole moments and densities.

Shock waves in dense hard disk fluids

Media composed of colliding hard disks (2D) or hard spheres (3D) serve as good approximations for the collective hydrodynamic description of gases, liquids and granular media. In the present study, the compressible hydrodynamics and shock dynamics are studied for a two-dimensional hard-disk medium at both the continuum and discrete particle level descriptions. For the continuum description, closed form analytical expressions for the inviscid hydrodynamic description, shock Hugoniot, isentropic exponent and shock jump conditions were obtained using the Helfand equation of state. The closed-form analytical solutions permitted us to gain physical insight into the role of the material’s density on its compressibility, i.e. how the medium compresses under mechanical loadings and sustains wave motion. Furthermore, the predictions were found in excellent agreement with calculations using the event driven molecular dynamics method involving 30,000 particles over the entire range of compressibility spanning the dilute ideal gas and liquid phases. In all cases, it was found that the energy imparted by the piston motion to the thermalized medium behind the propagating shock was quasi-independent of the medium’s packing fraction, with a correction vanishing with increasing shock Mach numbers.

Structural properties of hard disks in a narrow tube

Positional ordering of a two-dimensional fluid of hard disks is examined in tubes so narrowthat only nearest neighbor interactions take place. Using the exact transfer-matrix methodthe transverse and longitudinal pressure components and the correlation function aredetermined numerically. Fluid–solid phase transition does not occur even in the widesttube, where the method just loses its exactness, but the appearance of a dramaticchange in the equation of state and the longitudinal correlation function shows thatthe system undergoes a structural change from a fluid to a solid-like order. Thepressure components show that the collisions are dominantly longitudinal at lowdensities, while they are transverse in the vicinity of the close packing density. Thetransverse correlation function shows that the size of solid-like domains growsexponentially with increasing pressure and the correlation length diverges at closepacking. It is possible to find an analytically solvable model by expanding thecontact distance up to first order. The approximate model, which corresponds to asystem of hard parallel rhombuses, behaves very similarly to the system of harddisks.