Equilibrium phase behavior of polydisperse hard spheres

We calculate the phase behavior of hard spheres with size polydispersity, using accurate free energy expressions for the fluid and solid phases. Cloud and shadow curves, which determine the onset of phase coexistence, are found exactly by the moment free energy method, but we also compute the complete phase diagram, taking full account of fractionation effects. In contrast to earlier, simplified treatments we find no point of equal concentration between fluid and solid or re-entrant melting at higher densities. Rather, the fluid cloud curve continues to the largest polydispersity that we study (14%); from the equilibrium phase behavior a terminal polydispersity can thus only be defined for the solid, where we find it to be around 7%. At sufficiently large polydispersity, fractionation into several solid phases can occur, consistent with previous approximate calculations; we find in addition that coexistence of several solids with a fluid phase is also possible

The short-time self-diffusion coefficient of a sphere in a suspension of rigid rods

The short--time self diffusion coefficient of a sphere in a suspension of rigid rods is calculated in first order in the rod volume fraction. For low rod concentrations the correction to the Einstein diffusion constant of the sphere is a linear function of the rod volume fraction with the slope proportional to the equilibrium averaged mobility diminution trace of the sphere interacting with a single freely translating and rotating rod. The two--body hydrodynamic interactions are calculated using the so--called bead model in which the rod is replaced by a stiff linear chain of touching spheres. The interactions between spheres are calculated numerically using the multipole method. Also an analytical expression for the diffusion coefficient as a function of the rod aspect ratio is derived in the limit of very long rods. We show that in this limit the correction to the Einstein diffusion constant does not depend on the size of the tracer sphere. The higher order corrections depending on the applied model are computed numerically. An approximate expression is provided, valid for a wide range of aspect ratios.Comment: 11 pages, 6 figure

Critical behaviors of sheared frictionless granular materials near jamming transition

Critical behaviors of sheared dense and frictionless granular materials in the vicinity of the jamming transition are numerically investigated. From the extensive molecular dynamics simulation, we verify the validity of the scaling theory near the jamming transition proposed by Otsuki and Hayakawa (Prog. Theor. Phys., 121, 647 (2009)). We also clarify the critical behaviors of the shear viscosity and the pair correlation function based on both a phenomenology and the simulation.Comment: 13pages, 26 figure

Stacking Entropy of Hard Sphere Crystals

Classical hard spheres crystallize at equilibrium at high enough density. Crystals made up of stackings of 2-dimensional hexagonal close-packed layers (e.g. fcc, hcp, etc.) differ in entropy by only about $10^{-3}k_B$ per sphere (all configurations are degenerate in energy). To readily resolve and study these small entropy differences, we have implemented two different multicanonical Monte Carlo algorithms that allow direct equilibration between crystals with different stacking sequences. Recent work had demonstrated that the fcc stacking has higher entropy than the hcp stacking. We have studied other stackings to demonstrate that the fcc stacking does indeed have the highest entropy of ALL possible stackings. The entropic interactions we could detect involve three, four and (although with less statistical certainty) five consecutive layers of spheres. These interlayer entropic interactions fall off in strength with increasing distance, as expected; this fall-off appears to be much slower near the melting density than at the maximum (close-packing) density. At maximum density the entropy difference between fcc and hcp stackings is $0.00115 +/- 0.00004 k_B$ per sphere, which is roughly 30% higher than the same quantity measured near the melting transition.Comment: 15 page

Self-diffusion coefficients of charged particles: Prediction of Nonlinear volume fraction dependence

We report on calculations of the translational and rotational short-time self-diffusion coefficients $D^t_s$ and $D^r_s$ for suspensions of charge-stabilized colloidal spheres. These diffusion coefficients are affected by electrostatic forces and many-body hydrodynamic interactions (HI). Our computations account for both two-body and three-body HI. For strongly charged particles, we predict interesting nonlinear scaling relations $D^t_s\propto 1-a_t\phi^{4/3}$ and $D^r_s\propto 1-a_r\phi^2$ depending on volume fraction $\phi$, with essentially charge-independent parameters $a_t$ and $a_r$. These scaling relations are strikingly different from the corresponding results for hard spheres. Our numerical results can be explained using a model of effective hard spheres. Moreover, we perceptibly improve the known result for $D^t_s$ of hard sphere suspensions.Comment: 8 pages, LaTeX, 3 Postscript figures included using eps

Fluid-fluid phase separation in hard spheres with a bimodal size distribution

The effect of polydispersity on the phase behaviour of hard spheres is examined using a moment projection method. It is found that the Boublik-Mansoori-Carnahan-Starling-Leland equation of state shows a spinodal instability for a bimodal distribution if the large spheres are sufficiently polydisperse, and if there is sufficient disparity in mean size between the small and large spheres. The spinodal instability direction points to the appearance of a very dense phase of large spheres.Comment: 7 pages, 3 figures, moderately REVISED following referees' comments (original was 4 pages, 3 postscript figures

Fish, Flows, Isotopes and Food Webs: the Importance of Connectivity in Northern Australian Rivers

Northern Australia contains a rich freshwater biodiversity due largely to low levels of human impact. Most rivers remain unimpacted and free-flowing. The latter characteristic is important as it ensures that natural levels of connectivity throughout the riverine landscape exist and organisms and, importantly,carbon and nutrients, can be shifted between ecosystems and different parts of the landscape. This high degree of connectivity differs between rivers according to their flow regime however; most rivers of northern Australia are highly seasonal and flow intermittently. The present paper details the importance ofmaintaining connectivity within the river and between the river and its floodplain for the maintenance of species diversity and the structure of aquatic food webs. It draws upon large datasets concerning fish biodiversity and several foodweb studies using stable isotopes assembled or conducted with the TropicalRivers and Coastal Knowledge program to illustrate the importance of connectivit

Square root singularity in the viscosity of neutral colloidal suspensions at large frequencies

The asymptotic frequency $\omega$, dependence of the dynamic viscosity of neutral hard sphere colloidal suspensions is shown to be of the form $\eta_0 A(\phi) (\omega \tau_P)^{-1/2}$, where $A(\phi)$ has been determined as a function of the volume fraction $\phi$, for all concentrations in the fluid range, $\eta_0$ is the solvent viscosity and $\tau_P$ the P\'{e}clet time. For a soft potential it is shown that, to leading order steepness, the asymptotic behavior is the same as that for the hard sphere potential and a condition for the cross-over behavior to $1/\omega \tau_P$ is given. Our result for the hard sphere potential generalizes a result of Cichocki and Felderhof obtained at low concentrations and agrees well with the experiments of van der Werff et al, if the usual Stokes-Einstein diffusion coefficient $D_0$ in the Smoluchowski operator is consistently replaced by the short-time self diffusion coefficient $D_s(\phi)$ for non-dilute colloidal suspensions.Comment: 18 pages LaTeX, 1 postscript figur

Mixtures of Charged Colloid and Neutral Polymer: Influence of Electrostatic Interactions on Demixing and Interfacial Tension

The equilibrium phase behavior of a binary mixture of charged colloids and neutral, non-adsorbing polymers is studied within free-volume theory. A model mixture of charged hard-sphere macroions and ideal, coarse-grained, effective-sphere polymers is mapped first onto a binary hard-sphere mixture with non-additive diameters and then onto an effective Asakura-Oosawa model [S. Asakura and F. Oosawa, J. Chem. Phys. 22, 1255 (1954)]. The effective model is defined by a single dimensionless parameter -- the ratio of the polymer diameter to the effective colloid diameter. For high salt-to-counterion concentration ratios, a free-volume approximation for the free energy is used to compute the fluid phase diagram, which describes demixing into colloid-rich (liquid) and colloid-poor (vapor) phases. Increasing the range of electrostatic interactions shifts the demixing binodal toward higher polymer concentration, stabilizing the mixture. The enhanced stability is attributed to a weakening of polymer depletion-induced attraction between electrostatically repelling macroions. Comparison with predictions of density-functional theory reveals a corresponding increase in the liquid-vapor interfacial tension. The predicted trends in phase stability are consistent with observed behavior of protein-polysaccharide mixtures in food colloids.Comment: 16 pages, 5 figure

Phase Separation in Charge-Stabilized Colloidal Suspensions: Influence of Nonlinear Screening

The phase behavior of charge-stabilized colloidal suspensions is modeled by a combination of response theory for electrostatic interparticle interactions and variational theory for free energies. Integrating out degrees of freedom of the microions (counterions, salt ions), the macroion-microion mixture is mapped onto a one-component system governed by effective macroion interactions. Linear response of microions to the electrostatic potential of the macroions results in a screened-Coulomb (Yukawa) effective pair potential and a one-body volume energy, while nonlinear response modifies the effective interactions [A. R. Denton, \PR E {\bf 70}, 031404 (2004)]. The volume energy and effective pair potential are taken as input to a variational free energy, based on thermodynamic perturbation theory. For both linear and first-order nonlinear effective interactions, a coexistence analysis applied to aqueous suspensions of highly charged macroions and monovalent microions yields bulk separation of macroion-rich and macroion-poor phases below a critical salt concentration, in qualitative agreement with predictions of related linearized theories [R. van Roij, M. Dijkstra, and J.-P. Hansen, \PR E {\bf 59}, 2010 (1999); P. B. Warren, \JCP {\bf 112}, 4683 (2000)]. It is concluded that nonlinear screening can modify phase behavior but does not necessarily suppress bulk phase separation of deionized suspensions.Comment: 14 pages of text + 9 figure