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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., 21 pages, 6 figures

We report an accurate Monte Carlo calculation of the phase diagram and clustering properties of the restricted primitive model with non-additive hard-sphere diameters. At high density the positively non-additive fluid shows more clustering than the additive model and the negatively non-additive fluid shows less clustering than 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., 16 pages, 15 figures, 3 tables. arXiv admin note: text overlap with arXiv:1302.2473

The restricted primitive model with nonadditive hard-sphere diameters is shown to have interesting and peculiar clustering properties. We report accurate calculations of the cluster concentrations. Implementing efficient and ad hoc Monte Carlo algorithms we determine the effect of nonadditivity on both the clustering and the gas-liquid binodal. For negative nonadditivity, tending to the extreme case of completely overlapping unlike ions, the prevailing clusters are made of an even number of particles having zero total charge. For positive nonadditivity, the frustrated tendency to segregation of like particles and the reduced space available to the ions favors percolating clusters at high densities., Comment: 6 pages, 3 figures

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 (MC) simulations and find the main qualitative features of the critical behaviour 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 towards a more realistic description of globular proteins in solution., Comment: 47 pages, 18 figures, to appear on J. Chem. Phys

We calculate, through Monte Carlo numerical simulations, the partial total and direct correlation functions of the three dimensional symmetric Widom-Rowlinson mixture. We find that the differences between the partial direct correlation functions from simulation and from the Percus-Yevick approximation (calculated analytically by Ahn and Lebowitz) are well fitted by Gaussians. We provide an analytical expression for the fit parameters as function of the density. We also present Monte Carlo simulation data for the direct correlation functions of a couple of non additive hard sphere systems to discuss the modification induced by finite like diameters., 16 pages, 7 figures

A recently proposed connection between the threshold for the stability of the iterative solution of integral equations for the pair correlation functions of a classical fluid and the structural instability of the corresponding real fluid is carefully analyzed. Direct calculation of the Lyapunov exponent of the standard iterative solution of HNC and PY integral equations for the 1D hard rods fluid shows the same behavior observed in 3D systems. Since no phase transition is allowed in such 1D system, our analysis shows that the proposed one phase criterion, at least in this case, fails. We argue that the observed proximity between the numerical and the structural instability in 3D originates from the enhanced structure present in the fluid but, in view of the arbitrary dependence on the iteration scheme, it seems uneasy to relate the numerical stability analysis to a robust one-phase criterion for predicting a thermodynamic phase transition., 11 pages, 2 figures