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We use our quantum Gibbs ensemble Monte Carlo algorithm to perform computer experiments for the two-phase coexistence of a hydrogen-helium mixture. Our results are in quantitative agreement with the experimental results of Sneed, Streett, Sonntag, and Van Wylen. The difference between our results and the experimental ones is in all cases less than 15% relative to the experiment, reducing to less than 5% in the low helium concentration phase. At the gravitational inversion between the vapor and the liquid phase, at low temperatures and high pressures, the quantum effects become relevant. At extremely low temperature and pressure, the first component to show superfluidity is the helium in the vapor phase.

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A general class of nonadditive sticky-hard-sphere binary mixtures, where small and large spheres represent the solvent and the solute, respectively, is introduced. The solute-solute and solvent-solvent interactions are of hard-sphere type, while the solute-solvent interactions are of sticky-hard-sphere type with tunable degrees of size nonadditivity and stickiness. Two particular and complementary limits are studied using analytical and semi-analytical tools. The first case is characterized by zero nonadditivity, lending itself to a Percus-Yevick approximate solution from which the impact of stickiness on the spinodal curves and on the effective solute-solute potential is analyzed. In the opposite nonadditive case, the solvent-solvent diameter is zero and the model can then be reckoned as an extension of the well-known Asakura-Oosawa model with additional sticky solute-solvent interaction. This latter model has the property that its exact effective one-component problem involves only solute-solute pair potentials for size ratios such that a solvent particle fits inside the interstitial region of three touching solutes. In particular, we explicitly identify the three competing physical mechanisms (depletion, pulling, and bridging) giving rise to the effective interaction. Some remarks on the phase diagram of these two complementary models are also addressed through the use of the Noro-Frenkel criterion and a first-order perturbation analysis. Our findings suggest reentrance of the fluid-fluid instability as solvent density (in the first model) or adhesion (in the second model) is varied. Some perspectives in terms of the interpretation of recent experimental studies of microgels adsorbed onto large polystyrene particles are discussed.

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The binodal of a boson square-well fluid is determined as a function of the particle mass through a quantum Gibbs ensemble Monte Carlo algorithm devised by R. Fantoni and S. Moroni [J. Chem. Phys. (to be published)]. In the infinite mass limit we recover the classical result. As the particle mass decreases, the gas-liquid critical point moves at lower temperatures. We explicitly study the case of a quantum delocalization de Boer parameter close to the one of (4)He. For comparison, we also determine the gas-liquid coexistence curve of (4)He for which we are able to observe the binodal anomaly below the λ-transition temperature.

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We present a path integral Monte Carlo method which is the full quantum analogue of the Gibbs ensemble Monte Carlo method of Panagiotopoulos to study the gas-liquid coexistence line of a classical fluid. Unlike previous extensions of Gibbs ensemble Monte Carlo to include quantum effects, our scheme is viable even for systems with strong quantum delocalization in the degenerate regime of temperature. This is demonstrated by an illustrative application to the gas-superfluid transition of (4)He in two dimensions.

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Two theories for associating fluids recently used to study clustering in models for self-assembling patchy particles, Wertheim's and Bjerrum-Tani-Henderson theories, are carefully compared. We show that, for a fluid allowing only for dimerization, Wertheim theory is equivalent to the Bjerrum-Tani-Henderson theory neglecting intercluster correlations. Nonetheless, while the former theory is able to account for percolation and condensation, the latter is not. For the Bjerrum-Tani-Henderson theory we also rigorously prove the uniqueness of the solution for the cluster's concentrations and the reduction of the system of equations to a single one for a single unknown. We carry out Monte Carlo simulations of two simple models of dimerizing fluids and compare quantitatively the predictions of the two theories with the simulation data.

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The mutual entropic depletion force felt by two solute "big" hard spheres immersed in a binary mixture solvent of nonadditive "small" hard spheres is calculated as a function of the surface-to-surface distance by means of canonical Monte Carlo simulations and through a recently proposed rational-function approximation [R. Fantoni and A. Santos, Phys. Rev. E 84, 041201 (2011)]. Four representative scenarios are investigated: symmetric solute particles and the limit where one of the two solute spheres becomes a planar hard wall, in both cases with symmetric and asymmetric solvents. In all cases, the influence on the depletion force due to the nonadditivity in the solvent is determined in the mixed state. Comparison between results from the theoretical approximation and from the simulation shows a good agreement for surface-to-surface distances greater than the smallest solvent diameter.

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A class of binary mixtures of Janus fluids formed by colloidal spheres with the hydrophobic hemispheres constrained to point either up or down are studied by means of Gibbs ensemble Monte Carlo simulations and simple analytical approximations. These fluids can be experimentally realized by the application of an external static electrical field. The gas-liquid and demixing phase transitions in five specific models with different patch-patch affinities are analyzed. It is found that a gas-liquid transition is present in all the models, even if only one of the four possible patch-patch interactions is attractive. Moreover, provided the attraction between like particles is stronger than between unlike particles, the system demixes into two subsystems with different composition at sufficiently low temperatures and high densities.

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We report an accurate Monte Carlo calculation of the phase diagram and clustering properties of the restricted primitive model with nonadditive hard-sphere diameters. At high density the positively nonadditive fluid shows more clustering than in the additive model and the negatively nonadditive fluid shows less clustering than in the additive model; at low density the reverse scenario appears. A negative nonadditivity tends to favor the formation of neutrally charged clusters starting from the dipole. A positive nonadditivity favors the pairing of like ions at high density. The critical point of the gas-liquid phase transition moves at higher temperatures and higher densities for a negative nonadditivity and at lower temperatures and lower densities for a positive nonadditivity. The law of corresponding states does not seem to hold strictly. Our results can be used to interpret recent experimental works on room temperature ionic liquids.

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A recently proposed rational-function approximation [Phys. Rev. E 84, 041201 (2011)] for the structural properties of nonadditive hard spheres is applied to evaluate analytically (in Laplace space) the local density profiles of multicomponent nonadditive hard-sphere mixtures near a planar nonadditive hard wall. The theory is assessed by comparison with NVT Monte Carlo simulations of binary mixtures with a size ratio 1:3 in three possible scenarios: a mixture with either positive or negative nonadditivity near an additive wall, an additive mixture with a nonadditive wall, and a nonadditive mixture with a nonadditive wall. It is observed that, while the theory tends to underestimate the local densities at contact (especially in the case of the big spheres) it captures very well the initial decay of the densities with increasing separation from the wall and the subsequent oscillations.

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We study thermophysical properties of a Janus fluid with constrained orientations, using analytical techniques and numerical simulations. The Janus character is modeled by means of a Kern-Frenkel potential where each sphere has one hemisphere of square-well and the other of hard-sphere character. The orientational constraint is enforced by assuming that each hemisphere can only point either North or South with equal probability. The analytical approach hinges on a mapping of the above Janus fluid onto a binary mixture interacting via a "quasi" isotropic potential. The anisotropic nature of the original Kern-Frenkel potential is reflected by the asymmetry in the interactions occurring between the unlike components of the mixture. A rational-function approximation extending the corresponding symmetric case is obtained in the sticky limit, where the square-well becomes infinitely narrow and deep, and allows a fully analytical approach. Notwithstanding the rather drastic approximations in the analytical theory, this is shown to provide a rather precise estimate of the structural and thermodynamical properties of the original Janus fluid.

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Colloidosomes are created in the laboratory from a Pickering emulsion of water droplets in oil. The colloidosomes have approximately the same diameter and by choosing (hairy) particles of different diameters it is possible to control the particle density on the droplets. The experiment is performed at room temperature. The radial distribution function of the assembly of (primary) particles on the water droplet is measured in the laboratory and in a computer experiment of a fluid model of particles with pairwise interactions on the surface of a sphere.

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We construct a nonperturbative fully analytical approximation for the thermodynamics and the structure of nonadditive hard-sphere fluid mixtures. The method essentially lies in a heuristic extension of the Percus-Yevick solution for additive hard spheres. Extensive comparison with Monte Carlo simulation data shows a generally good agreement, especially in the case of like-like radial distribution functions.

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We propose a field-theoretical approach to a polymer system immersed in an ideal mixture of clustering centers. The system contains several species of these clustering centers with different functionality, each of which connects a fixed number segments of the chain to each other. The field theory is solved using the saddle point approximation and evaluated for dense polymer melts using the random phase approximation. We find a short-ranged effective intersegment interaction with strength dependent on the average segment density and discuss the structure factor within this approximation. We also determine the fractions of linkers of the different functionalities.

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The one-dimensional penetrable-square-well fluid is studied using both analytical tools and specialized Monte Carlo simulations. The model consists of a penetrable core characterized by a finite repulsive energy combined with a short-range attractive well. This is a many-body one-dimensional problem, lacking an exact analytical solution, for which the usual van Hove theorem on the absence of phase transition does not apply. We determine a high-penetrability approximation complementing a similar low-penetrability approximation presented in previous work. This is shown to be equivalent to the usual Debye-Hückel theory for simple charged fluids for which the virial and energy routes are identical. The internal thermodynamic consistency with the compressibility route and the validity of the approximation in describing the radial distribution function is assessed by a comparison against numerical simulations. The Fisher-Widom line separating the oscillatory and monotonic large-distance behaviors of the radial distribution function is computed within the high-penetrability approximation and compared with the opposite regime, thus providing a strong indication of the location of the line in all possible regimes. The high-penetrability approximation predicts the existence of a critical point and a spinodal line, but this occurs outside the applicability domain of the theory. We investigate the possibility of a fluid-fluid transition by the Gibbs ensemble Monte Carlo techniques, not finding any evidence of such a transition. Additional analytical arguments are given to support this claim. Finally, we find a clustering transition when Ruelle's stability criterion is not fulfilled. The consequences of these findings on the three-dimensional phase diagrams are also discussed.

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The linearized Debye-Hückel theory for liquid state is shown to provide thermodynamically consistent virial and energy routes for any potential and for any dimensionality. The importance of this result for bounded potentials is discussed.

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We study structural and thermophysical properties of a one-dimensional classical fluid made of penetrable spheres interacting via an attractive square-well potential. Penetrability of the spheres is enforced by reducing from infinite to finite the repulsive energy barrier in the pair potentials As a consequence, an exact analytical solution is lacking even in one dimension. Building upon previous exact analytical work in the low-density limit [A. Santos, R. Fantoni, and A. Giacometti, Phys. Rev. E 77, 051206 (2008)], we propose an approximate theory valid at any density and in the low-penetrable regime. By comparison with specialized Monte Carlo simulations and integral equation theories, we assess the regime of validity of the theory. We investigate the degree of inconsistency among the various routes to thermodynamics and explore the possibility of a fluid-fluid transition. Finally we locate the dependence of the Fisher-Widom line on the degree of penetrability. Our results constitute the first systematic study of penetrable spheres with attractions as a prototype model for soft systems.

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We discuss some interesting physical features stemming from our previous analytical study of a simple model of a fluid with dipolarlike interactions of very short range in addition to the usual isotropic Baxter potential for adhesive spheres. While the isotropic part is found to rule the global structural and thermodynamical equilibrium properties of the fluid, the weaker anisotropic part gives rise to an interesting short-range local ordering of nearly spherical condensation clusters, containing short portions of chains having nose-to-tail parallel alignment, which runs antiparallel to adjacent similar chains.

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We consider an anisotropic version of Baxter's model of "sticky hard spheres," where a nonuniform adhesion is implemented by adding, to an isotropic surface attraction, an appropriate "dipolar sticky" correction (positive or negative, depending on the mutual orientation of the molecules). The resulting nonuniform adhesion varies continuously, in such a way that in each molecule one hemisphere is "stickier" than the other. We derive a complete analytic solution by extending a formalism [M. S. Wertheim, J. Chem. Phys. 55, 4281 (1971)] devised for dipolar hard spheres. Unlike Wertheim's solution, which refers to the "mean spherical approximation," we employ a Percus-Yevick closure with orientational linearization, which is expected to be more reliable. We obtain analytic expressions for the orientation-dependent pair correlation function g(1,2) . Only one equation for a parameter K has to be solved numerically. We also provide very accurate expressions which reproduce K as well as some parameters, Lambda1 and Lambda2, of the required Baxter factor correlation functions with a relative error smaller than 1%. We give a physical interpretation of the effects of the anisotropic adhesion on the g(1,2) . The model could be useful for understanding structural ordering in complex fluids within a unified picture.

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We introduce a model of attractive penetrable spheres by adding a short-range attractive square well outside a penetrable core, and we provide a detailed analysis of structural and thermodynamical properties in one dimension using the exact impenetrable counterpart as a starting point. The model is expected to describe star polymers in regimes of good and moderate solvent under dilute conditions. We derive the exact coefficients of a low-density expansion up to second order for the radial distribution function and up to fourth order in the virial expansion. These exact results are used as a benchmark to test the reliability of approximate theories (Percus-Yevick and hypernetted chain). Notwithstanding the lack of an exact solution for arbitrary densities, our results are expected to be rather precise within a wide range of temperatures and densities. A detailed analysis of some limiting cases is carried out. In particular, we provide a complete solution of the sticky penetrable-sphere model in one dimension up to the same order in density. The issue of Ruelle's thermodynamics stability is analyzed and the region of a well-defined thermodynamic limit is identified.

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We consider a fluid of hard spheres bearing one or two uniform circular adhesive patches, distributed so as not to overlap. Two spheres interact via a "sticky" Baxter potential if the line joining the centers of the two spheres intersects a patch on each sphere, and via a hard sphere potential otherwise. We analyze the location of the fluid-fluid transition and of the percolation line as a function of the size of the patch (the fractional coverage of the sphere's surface) and of the number of patches within a virial expansion up to third order and within the first two terms (C0 and C1) of a class of closures Cn hinging on a density expansion of the direct correlation function. We find that the locations of the two lines depend sensitively on both the total adhesive coverage and its distribution. The treatment is almost fully analytical within the chosen approximate theory. We test our findings by means of specialized Monte Carlo simulations and find the main qualitative features of the critical behavior to be well captured in spite of the low density perturbative nature of the closure. The introduction of anisotropic attractions into a model suspension of spherical particles is a first step toward a more realistic description of globular proteins in solution.