The hypernetted chain/mean spherical approximation (HNC/MSA) integral equation for a totally asymmetric primitive model electrolyte around a spherical macroparticle is obtained and solved numerically in the case of size-asymmetric systems. The ensuing radial distribution functions show a very good agreement when compared to our Monte Carlo and molecular-dynamics simulations for spherical geometry and with respect to previous anisotropic reference HNC calculations in the planar limit. We report an analysis of the potential versus charge relationship, radial distribution functions, mean electrostatic potential, and cumulative reduced charge for representative examples of 1:1 and 2:2 salts with a size-asymmetry ratio of 2. Our results are collated with those of the modified Gouy-Chapman (MGC) and unequal radius modified Gouy-Chapman (URMGC) theories and with those of HNC/MSA in the restricted primitive model (RPM) to assess the importance of size-asymmetry effects. One of the most striking characteristics found is that, contrary to the general belief, away from the point of zero charge the properties of an asymmetric electrical double layer (EDL) are not those corresponding to a symmetric electrolyte with the size and charge of the counterion, i.e., counterions do not always dominate. This behavior suggests the existence of a new phenomenology in the EDL that genuinely belongs to a more realistic size-asymmetric model where steric correlations are taken into account consistently. Such novel features cannot be described by traditional mean-field theories such as MGC, URMGC, or even by enhanced formalisms, such as HNC/MSA, if they are based on the RPM.

Colloidal suspensions of Laponite clay platelets are studied by means of Brownian dynamics simulations. The platelets carry discrete charged sites which interact via a Yukawa potential. As in the paper by S. Kutter et al. [J. Chem. Phys. 112, 311 (2000)], two models are considered. In the first one all surface sites are identically negative charged, whereas in the second one, rim charges of opposite sign are included. These models mimic the behavior of the Laponite particles in different media. They are employed in a series of simulations for different Laponite concentrations and for two values of the Debye length. For the equilibrium states, the system structure is studied by center-to-center and orientational pair distribution functions. Long-time translational and rotational self-diffusion coefficients are computed by two different methods, which yield very similar results.

A recently developed theory of collective diffusion in colloidal suspensions is tested regarding the quantitative accuracy of its description of the dynamics of monodisperse model colloidal systems without hydrodynamic interactions. The idea is to exhibit the isolated effects of the direct interactions, which constitute the main microscopic relaxation mechanism, in the absence of other effects, such as hydrodynamic interactions. Here we compare the numerical solution of the fully self-consistent theory with the results of Brownian dynamics simulation of the van Hove function G(r,t) and/or the intermediate scattering function F(k,t) of four simple model systems. Two of them are representative of short-ranged soft-core repulsive interactions [(sigma/r)(mu), with mu>>1], in two and in three dimensions. The other two involve long-ranged repulsive forces in two (dipolar, r(-3) potential) and in three (screened Coulomb, or repulsive Yukawa interactions) dimensions. We find that the theory, without any sort of adjustable parameters or rescaling prescriptions, provides an excellent approximate description of the collective dynamics of these model systems, particularly in the short- and intermediate-time regimes. We also compare our results with those of the single exponential approximation and with the competing mode-mode coupling theory.

In this work the Na-montmorillonite hydrates are studied for different burial depths by means of hybrid Monte Carlo (HMC) and molecular dynamics (MD) simulations. The HMC simulations, performed using a NP zz T ensemble, allow us to study the interlaminar space distance, structural properties, and thermodynamical properties, such as the water chemical potential. The latter quantifies the system affinity for water, and hence, it is useful for determining the most probable hydration states for a given basin condition. For increasing burial depth, we found many agreements with experimental results such as a tendency to dehydration, an increasing disorder of the interlaminar space, and a constant coordination number for the first water shell around Na+. The MD simulations, on the other hand, were performed employing a microcanonical ensemble, from which the diffusion coefficients for water and Na+ were also investigated for high-temperature and high-pressure conditions.

In this work, we demonstrate the dynamic equivalence between the members of the family of Brownian fluids whose particles interact through strongly repulsive radially symmetric soft-core potentials. We specifically consider pair potentials proportional to inverse powers of (r/sigma). This equivalence is the dynamic extension of the static equivalence between all these pair potentials and the hard-sphere fluid, assumed in the treatment of soft-core reference potentials in the classical (Weeks-Chandler-Andersen or Barker-Henderson) perturbation theories of simple liquids. In contrast with the strict hard-sphere Brownian system, in the case of soft-sphere potentials the conventional Brownian dynamics algorithm is indeed well defined. We find that, except for small values of nu, and/or very short times, the dynamic properties of all these systems collapse into a single universal curve, upon a well-defined rescaling of the time and distance variables. This family of systems includes the hard-sphere limit. This observation permits a conceptually simple, new, and accurate Brownian dynamics algorithm to simulate the dynamic properties of the hard-sphere model dispersion without hydrodynamic interactions. Such an algorithm consists of the straightforward rescaling of the Brownian-dynamics simulated properties of any of the dynamically equivalent soft-sphere systems.