Using the second virial coefficient as physical criterion to map the hard-sphere potential onto a continuous potential.

In the same sense as in the extended law of corresponding states [M. Noro and D. Frenkel, J. Chem. Phys. 113, 2941 (2000)], we propose the use of the second virial coefficient to map the hard-sphere potential onto a continuous potential. We show that this criterion provides accurate results when the continuous potential is used, for example, in computer simulations to reproduce the physical properties of systems with hard-core interactions. We also demonstrate that this route is straightforwardly applicable to any spatial dimension, does not depend on the particle density and, from a numerical point of view, is easy to implement.

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.

Short-time dynamics of monomers and dimers in quasi-two-dimensional colloidal mixtures.

We report on the short-time dynamics in colloidal mixtures made up of monomers and dimers highly confined between two glass plates. At low concentrations, the experimental measurements of colloidal motion agree well with the solution of the Navier-Stokes equation at low Reynolds numbers; the latter takes into account the increase in the drag force on a colloidal particle due to wall-particle hydrodynamic forces. More importantly, we find that the ratio of the short-time diffusion coefficient of the monomer and that of the center of mass of the dimmer is almost independent of both the dimer molar fraction, x_{d}, and the total packing fraction, ϕ, up to ϕ≈0.5. At higher concentrations, this ratio displays a small but systematic increase. A similar physical scenario is observed for the ratio between the parallel and the perpendicular components of the short-time diffusion coefficients of the dimer. This dynamical behavior is corroborated by means of molecular dynamics computer simulations that include explicitly the particle-particle hydrodynamic forces induced by the solvent. Our results suggest that the effects of colloid-colloid hydrodynamic interactions on the short-time diffusion coefficients are almost identical and factorable in both species.

Brownian motion of a nano-colloidal particle: the role of the solvent.

Brownian motion is a feature of colloidal particles immersed in a liquid-like environment. Usually, it can be described by means of the generalised Langevin equation (GLE) within the framework of the Mori theory. In principle, all quantities that appear in the GLE can be calculated from the molecular information of the whole system, i.e., colloids and solvent molecules. In this work, by means of extensive Molecular Dynamics simulations, we study the effects of the microscopic details and the thermodynamic state of the solvent on the movement of a single nano-colloid. In particular, we consider a two-dimensional model system in which the mass and size of the colloid are two and one orders of magnitude, respectively, larger than the ones associated with the solvent molecules. The latter ones interact via a Lennard-Jones-type potential to tune the nature of the solvent, i.e., it can be either repulsive or attractive. We choose the linear momentum of the Brownian particle as the observable of interest in order to fully describe the Brownian motion within the Mori framework. We particularly focus on the colloid diffusion at different solvent densities and two temperature regimes: high and low (near the critical point) temperatures. To reach our goal, we have rewritten the GLE as a second kind Volterra integral in order to compute the memory kernel in real space. With this kernel, we evaluate the momentum-fluctuating force correlation function, which is of particular relevance since it allows us to establish when the stationarity condition has been reached. Our findings show that even at high temperatures, the details of the attractive interaction potential among solvent molecules induce important changes in the colloid dynamics. Additionally, near the critical point, the dynamical scenario becomes more complex; all the correlation functions decay slowly in an extended time window, however, the memory kernel seems to be only a function of the solvent density. Thus, the explicit inclusion of the solvent in the description of Brownian motion allows us to better understand the behaviour of the memory kernel at those thermodynamic states near the critical region without any further approximation. This information is useful to elaborate more realistic descriptions of Brownian motion that take into account the particular details of the host medium.

Structural transitions and long-time self-diffusion of interacting colloids confined by a parabolic potential.

We report on the ordering and dynamics of interacting colloidal particles confined by a parabolic potential. By means of Brownian dynamics simulations, we find that by varying the magnitude of the trap stiffness, it is possible to control the dimension of the system and, thus, explore both the structural transitions and the long-time self-diffusion coefficient as a function of the degree of confinement. We particularly study the structural ordering in the directions perpendicular and parallel to the confinement. Further analysis of the local distribution of the first-neighbors layer allows us to identify the different structural phases induced by the parabolic potential. These results are summarized in a structural state diagram that describes the way in which the colloidal suspension undergoes a structural re-ordering while increasing the confinement. To fully understand the particle dynamics, we take into account hydrodynamic interactions between colloids; the parabolic potential constricts the available space for the colloids, but it does not act on the solvent. Our findings show a non-linear behavior of the long-time self-diffusion coefficient that is associated to the structural transitions induced by the external field.

Hydrodynamic correlations in three-particle colloidal systems in harmonic traps.

We report on the hydrodynamic correlations between colloids immersed in a low Reynolds number fluid. We consider colloidal arrays composed of three particles; each colloid is trapped in a single harmonic potential and interacts with the other colloids only via hydrodynamic forces. We focus on the role of a third body in the two-body correlation functions. We give special attention to a collinear configuration of particles, although the salient features of an equilateral triangle configuration are outlined. The correlation functions are computed both by means of Brownian dynamics simulations, and by solving analytically and numerically the Langevin equation under the assumption of constant diffusion tensor; this approximation is validated through computer simulations. We explicitly show that the presence of a third body affects the auto- and cross-correlation functions and that their behaviour, in some specific conditions, can be different from that commonly seen in a two-particle system. In particular, we have found that the auto-correlation functions show a slower decay, while the cross-correlation ones exhibit a temporal shift and a weaker amplitude. Moreover, an unexpected behaviour related to a positive correlation and associated with the appearance of new dynamical modes is observed in the case of the collinear array of three particles. This interesting effect might be used to tune the degree of hydrodynamic correlation in few-body colloidal systems.

Ordering and single-file diffusion in colloidal systems.

The structural properties and the single-file diffusion in one-dimensional interacting colloidal systems are studied by means of Brownian dynamics simulations. We consider three types of particle interactions, namely, Weeks-Chandler-Andersen, screened Coulomb, and superparamagnetic potentials. We find that, regardless of the interaction potential, at low densities particles are distributed in a typical fluidlike structure and at higher densities or potential strengths become spatially correlated at long-distances. Particularly, our findings demonstrate that one-dimensional systems, with particles interacting repulsively, show common structural and dynamical behaviors at the boundary in which the degree of ordering changes dramatically; the main peak of the static structure factor becomes highly narrow with a height of S(c)≈7, whereas the reduced mobility factor F, which is associated with the single-file diffusion at long-times or long wavelengths, reaches values F(∗)≈0.1. These features are analyzed and discussed in the context of a local order-disorder transition.

Diffusion in two-dimensional colloidal systems on periodic substrates.

We study the diffusive behavior of two-dimensional charged colloidal suspensions subjected to a sinusoidal substrate by means of Brownian dynamics simulations. We mainly focus on the dependence of the mean-square displacement on the substrate strength. Our findings show a variation in the particle diffusion due to a substrate-induced distortion of the dynamic cage of nearest-neighbor colloids. This mechanism leads to a transition from normal diffusion at short times to subdiffusion on intermediate time scales. However, at long times normal diffusion is recovered. We also show that the variation in the long-time self-diffusion coefficient may be associated with the freezing and re-entrant melting transitions.