Size effect and stability of polarized fluid phases.

The existence of a ferroelectric fluid phase for systems of 1000-2000 dipolar hard or soft spheres is well established by numerical simulations. Theoretical approaches proposed to determine the stability of such a phase are either in qualitative agreement with the simulation results or disagree with them. Experimental results for systems of molecules or particles with large electric or magnetic dipole moments are also inconclusive. As a contribution to the question of existence and stability of a fluid ferroelectric phase this simulation work considers system sizes of the order of 10 000 particles, thus an order of magnitude larger than those used in previous studies. It shows that although ferroelectricity is not affected by an increase of system size, different spatial arrangements of the dipolar hard spheres in such a phase are possible whose free energies seem to differ only marginally.

Influence of short range potential on field induced chain aggregation in low density dipolar particles.

We investigate, by Monte Carlo simulation, the effect of the steepness of the short range repulsive potential on mesostructure formation in dipolar particles submitted to a strong external field. Columnar clusters made of several dipolar chains are only observed when the short-range potential is sufficiently steep. The confinement of the dipolar liquid in a slit geometry instead of bulk conditions suppresses the formation of columns.

Low density mesostructures of confined dipolar particles in an external field.

Mesostructures formed by dipolar particles confined between two parallel walls and subjected to an external field are studied by Monte Carlo simulations. The main focus of the work is the structural behavior of the Stockmayer fluid in the low density regime. The dependence of cluster thickness and ordering is estimated as a function of density and wall separation, the two most influential parameters, for large dipole moments and high field strengths. The great sensitivity of the structure to details of the short-range part of the interactions is pointed out. In particular, the attractive part of the Lennard-Jones potential is shown to play a major role in driving chain aggregation. The effect of confinement, evaluated by comparison with results for a bulk system, is most pronounced for a short range hard sphere potential. No evidence is found for a novel "gel-like" phase recently uncovered in low density dipolar colloidal suspensions [A. K. Agarwal and A. Yethiraj, Phys. Rev. Lett. 102, 198301 (2009)].

A computational study of electrolyte adsorption in a simple model for intercalated clays.

A pillared interlayered clay is represented by a two-dimensional quenched charged disordered medium, in which the pillar configuration is produced by the quench of a two-dimensional electrolyte and the subsequent removal of the anions (that act as a template). The cation charge is counterbalanced by a neutralizing background that is an ideal representation of the layer's negative charge in the experimental system. In this paper we investigate the adsorption of electrolyte particles in this charged disordered medium resorting both to the use of the replica Ornstein-Zernike equation in the hypernetted chain approximation and grand canonical Monte Carlo simulations. The theoretical approach qualitatively reproduces the simulated behavior of the adsorbed fluids. Theoretical estimates of the material porosities obtained for various types of pillar distributions are in good agreement with the simulation. We investigate the influence of the matrix on correlation functions and adsorption isotherms.

Self-organization of confined dipolar particles in a parallel field.

Monte Carlo simulations of a Stockmayer fluid confined between two parallel walls are performed to investigate self-organization of magnetic nanocrystals in a field parallel to the walls as a function of density, field strength, and wall separation. In order to study the formation of mesoscopic structures, a large number of up to 12,000 particles have to be used. The particles organize into periodically spaced cylindrical-like columns whose width typically varies between 5 and 9 particle diameters at low density. At small heights the columns are quenched due to the parallel walls, while larger wall separations can accommodate several layers of columns in good agreement with experiments. An increase in density entails a clear increase in column thickness, whereas an increase in field strength seems to have the opposite effect.

Mesoscopic void structures in cobalt nanocrystal films formed from drying concentrated colloidal solutions.

Here we report the formation of void (hole) structures when concentrated colloidal solutions of magnetic nanocrystals are subjected to a magnetic field during slow evaporation. This presents a new type of solid mesostructure obtained by self-assembly of nanocrystals. The voids are characterized by a cylindrical shape with either circular or elliptical base. We show that the morphology of these patterns is essentially controlled by the fraction of the volume occupied by the magnetic phase to the total volume of the film. Monte Carlo simulations carried out using a Stockmayer fluid model agree remarkably well with the experiments for the formation of void structures in the range of considered volume fractions.

Self-organization of magnetic nanoparticles: a Monte Carlo study.

To understand the self-organization of magnetic nanocrystals in an applied field, we perform Monte Carlo simulations of Stockmayer fluids confined between two parallel walls. The system is examined in the gas-liquid coexistence region of its phase diagram and the field is applied perpendicular to the walls. Gibbs ensemble simulations are carried out to determine the phase coexistence curves of the confined Stockmayer fluid. In canonical simulations, different types of organizations appear dependent on particle density: columns, walls, and elongated and spherical holes. The morphology and size of structures are in good agreement with results obtained by free energy minimization and experiments. The influence of a distribution of particle sizes on the particle organization is investigated.

Orientational order in high density dipolar hard sphere fluids.

Taking advantage of recent estimates, by one of us, of the critical temperature of the isotropic-ferroelectric transition of high density dipolar hard spheres, we performed new Monte Carlo simulations in the close vicinity of these estimates and applied histogram reweighting methods to obtain refined values of the critical temperatures from the crossing of the fourth-order cumulant for different system sizes. The ferroelectric line is determined in the density range rho*=0.80-0.95, and the onset of columnar ordering is located.

The ferroelectric transition of dipolar hard spheres.

We investigate by Monte Carlo simulation the size dependence of the variation of the polarization and the dielectric constant with temperature for dipolar hard spheres at the two densities rho sigma3=0.80 and 0.88. From the crossing of the fourth-order cumulant for different system sizes first more precise estimates of the ferroelectric transition temperatures are obtained. Theoretical approaches, when predicting an ordering transition, are shown to generally overestimate the critical temperature.

Structure and thermodynamics of a ferrofluid monolayer

We model a disordered planar monolayer of paramagnetic spherical particles, or ferrofluid, as a two-dimensional fluid of hard spheres with embedded three-dimensional magnetic point dipoles. This model, in which the orientational degrees of freedom are three dimensional while particle positions are confined to a plane, can be taken as a crude representation of a colloidal suspension of superparamagnetic particles confined in a water/air interface, a system that has recently been studied experimentally. In this paper, we propose an Ornstein-Zernike integral equation approach capable of describing the structure of this highly inhomogeneous fluid, including the effects of an external magnetic field. The method hinges on the use of specially tailored orthogonal polynomials whose weight function is precisely the one-particle distribution function that describes the surface- and field-induced anisotropy. The results obtained for various particle densities and external fields are compared with Monte Carlo simulations, illustrating the capability of the inhomogeneous Ornstein-Zernike equation and the proposed solution scheme to yield a detailed and accurate description of the spatial and orientational structure for this class of systems. For comparison, results from density-functional theory in the modified mean-field approximation are also presented; this latter approach turns out to yield at least qualitatively correct results.