Gabriel Pérez-Ángel

Dynamic equivalence between atomic and colloidal liquids

We show that the kinetic-theoretical self-diffusion coefficient of an atomic fluid plays the same role as the short-time self-diffusion coefficient DS in a colloidal liquid, in the sense that the dynamic properties of the former, at times much longer than the mean free time, and properly scaled with DS, will be indistinguishable from those of a colloidal liquid with the same interaction potential. One important consequence of such dynamic equivalence is that the ratio DL/DS of the long-time to the short-time self-diffusion coefficients must then be the same for both an atomic and a colloidal system characterized by the same inter-particle interactions. This naturally extends to atomic fluids a well-known dynamic criterion for freezing of colloidal liquids (L?wen H. et al., Phys. Rev. Lett., 70 (1993) 1557). We corroborate these predictions by comparing molecular and Brownian dynamics simulations on the hard-sphere system and on other soft-sphere model systems, representative of the ?hard-sphere?dynamic universality class.

Equilibration of concentrated hard-sphere fluids.

We report a systematic molecular dynamics study of the isochoric equilibration of hard-sphere fluids in their metastable regime close to the glass transition. The thermalization process starts with the system prepared in a nonequilibrium state with the desired final volume fraction ϕ for which we can obtain a well-defined nonequilibrium static structure factor S(0)(k;ϕ). The evolution of the α-relaxation time τ(α)(k) and long-time self-diffusion coefficient D(L) as a function of the evolution time t(w) is then monitored for an array of volume fractions. For a given waiting time the plot of τ(α)(k;ϕ,t(w)) as a function of ϕ exhibits two regimes corresponding to samples that have fully equilibrated within this waiting time [ϕ≤ϕ(c)(t(w))] and to samples for which equilibration is not yet complete [ϕ≥ϕ(c)(t(w))]. The crossover volume fraction ϕ(c)(t(w)) increases with t(w) but seems to saturate to a value ϕ(a)≡ϕ(c)(t(w)→∞)≈0.582. We also find that the waiting time t(w)(eq)(ϕ) required to equilibrate a system grows faster than the corresponding equilibrium relaxation time, t(w)(eq)(ϕ)≈0.27[τ(α)(eq)(k;ϕ)](1.43), and that both characteristic times increase strongly as ϕ approaches ϕ(a), thus suggesting that the measurement of equilibrium properties at and above ϕ(a) is experimentally impossible.

Demixing transition, structure, and depletion forces in binary mixtures of hard-spheres: The role of bridge functions

Asymmetric binary mixtures of hard-spheres exhibit several interesting thermodynamic phenomena, such as multiple kinds of glassy states. When the degrees of freedom of the small spheres are integrated out from the description, their effects are incorporated into an effective pair interaction between large spheres known as the depletion potential. The latter has been widely used to study both the phase behavior and dynamic arrest of the big particles. Depletion forces can be accounted for by a contraction of the description in the multicomponent Ornstein-Zernike equation [R. Castañeda-Priego, A. Rodríguez-López, and J. M. Méndez-Alcaraz, Phys. Rev. E 73, 051404 (2006)]. Within this theoretical scheme, an approximation for the difference between the effective and bare bridge functions is needed. In the limit of infinite dilution, this difference is irrelevant and the typical Asakura-Osawa depletion potential is recovered. At higher particle concentrations, however, this difference becomes important, especially where the shell of first neighbors is formed, and, as shown here, cannot be simply neglected. In this work, we use a variant of the Verlet expression for the bridge functions to highlight their importance in the calculation of the depletion potential at high densities and close to the spinodal decomposition. We demonstrate that the modified Verlet closure predicts demixing in binary mixtures of hard spheres for different size ratios and compare its predictions with both liquid state and density functional theories, computer simulations, and experiments. We also show that it provides accurate correlation functions even near the thermodynamic instability; this is explicitly corroborated with results of molecular dynamics simulations of the whole mixture. Particularly, our findings point toward a possible universal behavior of the depletion potential around the spinodal line.

Note: depletion potentials in non-additive asymmetric binary mixtures of hard-spheres.

Cesar D. Estrada-Alvarez,1 Erik Lopez-Sanchez,1 Gabriel Perez-Angel,2 Pedro Gonzalez-Mozuelos,3 Jose Miguel Mendez-Alcaraz,3 and Ramon Castaneda-Priego1,a) 1Division de Ciencias e Ingenierias, University of Guanajuato, Loma del Bosque 103, 37150 Leon, Mexico 2Departamento de Fisica Aplicada, Cinvestav, Unidad Merida, Apartado Postal 73 Cordemex, 97310 Merida, Yucatan, Mexico 3Departamento de Fisica, Cinvestav, Av. IPN 2508, Col. San Pedro Zacatenco, 07360 Mexico City, Mexico

Crossover from equilibration to aging: Nonequilibrium theory versus simulations

Understanding glasses and the glass transition requires comprehending the nature of the crossover from the ergodic (or equilibrium) regime, in which the stationary properties of the system have no history dependence, to the mysterious glass transition region, where the measured properties are nonstationary and depend on the protocol of preparation. In this work we use nonequilibrium molecular dynamics simulations to test the main features of the crossover predicted by the molecular version of the recently developed multicomponent nonequilibrium self-consistent generalized Langevin equation theory. According to this theory, the glass transition involves the abrupt passage from the ordinary pattern of full equilibration to the aging scenario characteristic of glass-forming liquids. The same theory explains that this abrupt transition will always be observed as a blurred crossover due to the unavoidable finiteness of the time window of any experimental observation. We find that within their finite waiting-time window, the simulations confirm the general trends predicted by the theory.

One-dimensional Gaussian-core fluid: ordering and crossover from normal diffusion to single-file dynamics

The peculiarity of a bounded pair potential in combination with strong confinement brings some quite interesting new phenomenology in the structure and dynamics of one-dimensional colloidal systems. Such behaviour is atypical in comparison with colloidal systems interacting with potentials that diverge at the origin. In this contribution, by means of molecular dynamics simulations, a confined one-dimensional model of particles interacting via a Gaussian-core pair potential is studied. We explore the effects of confinement, density and temperature on the structural and dynamical correlation functions. Our findings indicate that the static and dynamic liquid-state anomalies already reported in open systems are also present in this 1D model system. Using the radial distribution function and the static structure factor to characterise the spatial ordering, it is observed that the system remains fluid at all densities. However, when the reduced temperature is above 0.03, it displays typical features of a liquid regime, i.e., there exist short-range spatial correlations among particles. In contrast, at lower temperatures and densities, where the particle-particle interaction dominates, the system behaves structurally and dynamically similar to a hard-core repulsive system. In such a region, interestingly, there is a crossover from a liquid to a solid-like regime. At any given temperature, the system undergoes a sort of reentrant structural behaviour as the density increases. At either high densities or temperatures, particle correlations vanish, thus, the system exhibits structural and dynamical properties similar to those of an ideal gas. To examine a possible correlation between the structural anomalies and the diffusive behaviour, the mean-square displacement and the self-intermediate scattering function are also computed. From these observables, we establish the thermodynamic phase-space points where the dynamical behaviour is non-monotonic. In conjunction with the observed anomalous diffusion, we have found a dynamical crossover from single-file diffusion, which is characteristic of one-dimensional systems with a well-defined hard-core, to the ordinary Fickian diffusion present in open systems.

Stress distribution in two-dimensional silos

Simulations of a polydispersed two-dimensional silo were performed using molecular dynamics, with different numbers of grains reaching up to 64 000, verifying numerically the model derived by Janssen and also the main assumption that the walls carry part of the weight due to the static friction between grains with themselves and those with the silos walls. We vary the friction coefficient, the radii dispersity, the silo width, and the size of grains. We find that the Janssens model becomes less relevant as the the silo width increases since the behavior of the stresses becomes more hydrostatic. Likewise, we get the normal and tangential stress distribution on the walls evidencing the existence of points of maximum stress. We also obtained the stress matrix with which we observe zones of concentration of load, located always at a height around two thirds of the granular columns. Finally, we observe that the size of the grains affects the distribution of stresses, increasing the weight on the bottom and reducing the normal stress on the walls, as the grains are made smaller (for the same total mass of the granulate), giving again a more hydrostatic and therefore less Janssen-type behavior for the weight of the column.

Clustering-Induced Attraction in Granular Mixtures of Rods and Spheres

Depletion-induced aggregation of rods enhanced by clustering is observed to produce a novel model of attractive pairs of rods separated by a line of spheres in a quasi-2D, vertically-shaken, granular gas of rods and spheres. We show that the stability of these peculiar granular aggregates increases as a function of shaking intensity. Velocity distributions of spheres inside and outside of a pair of rods trapping a line of spheres show a clear suppression of the momentum acquired by the trapped spheres. The condensed phase formed between the rods is caused by a clustering instability of the trapped spheres, enhanced by a vertical guidance produced by the confining rods. The liberated area corresponding to direct excluded-volume pairs and indirect depletion-aggregated pairs is measured as a function of time. The stability of rod pairs mediated by spheres reveals an attraction comparable in strength to the one purely induced by depletion forces.

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.

Self-consistent generalized Langevin equation theory of the dynamics of multicomponent atomic liquids

A fundamental challenge of the theory of liquids is to understand the similarities and differences in the macroscopic dynamics of both colloidal and atomic liquids, which originate in the (Newtonian or Brownian) nature of the microscopic motion of their constituents. Starting from the recently discovered long-time dynamic equivalence between a colloidal and an atomic liquid that share the same interparticle pair potential, in this work we develop a self-consistent generalized Langevin equation theory for the dynamics of equilibrium multicomponent atomic liquids, applicable as an approximate but quantitative theory describing the long-time diffusive dynamical properties of simple equilibrium atomic liquids. When complemented with a Gaussian-like approximation, this theory is also able to provide a reasonable representation of the passage from a ballistic to diffusive behavior. We illustrate the applicability of the resulting theory with three particular examples, namely, a monodisperse and a polydisperse monocomponent hard-sphere liquid and a highly size-asymmetric binary hard-sphere mixture. To assess the quantitative accuracy of our results, we perform event-driven molecular dynamics simulations, which corroborate the general features of the theoretical predictions.