Phase behavior of the modified-Yukawa fluid and its sticky limit.

Simple model systems with short-range attractive potentials have turned out to play a crucial role in determining theoretically the phase behavior of proteins or colloids. However, as pointed out by D. Gazzillo [J. Chem. Phys. 134, 124504 (2011)], one of these widely used model potentials, namely, the attractive hard-core Yukawa potential, shows an unphysical behavior when one approaches its sticky limit, since the second virial coefficient is diverging. However, it is exactly this second virial coefficient that is typically used to depict the experimental phase diagram for a large variety of complex fluids and that, in addition, plays an important role in the Noro-Frenkel scaling law [J. Chem. Phys. 113, 2941 (2000)], which is thus not applicable to the Yukawa fluid. To overcome this deficiency of the attractive Yukawa potential, D. Gazzillo has proposed the so-called modified hard-core attractive Yukawa fluid, which allows one to correctly obtain the second and third virial coefficients of adhesive hard-spheres starting from a system with an attractive logarithmic Yukawa-like interaction. In this work we present liquid-vapor coexistence curves for this system and investigate its behavior close to the sticky limit. Results have been obtained with the self-consistent Ornstein-Zernike approximation (SCOZA) for values of the reduced inverse screening length parameter up to 18. The accuracy of SCOZA has been assessed by comparison with Monte Carlo simulations.

Phase behavior of colloids and proteins in aqueous suspensions: theory and computer simulations.

The fluid phase behavior of colloidal suspensions with short-range attractive interactions is studied by means of Monte Carlo computer simulations and two theoretical approximations, namely, the discrete perturbation theory and the so-called self-consistent Ornstein-Zernike approximation. The suspensions are modeled as hard-core attractive Yukawa (HCAY) and Asakura-Oosawa (AO) fluids. A detailed comparison of the liquid-vapor phase diagrams obtained through different routes is presented. We confirm Noro-Frenkel's extended law of scaling according to which the properties of a short-ranged fluid at a given temperature and density are independent of the detailed form of the interaction, but just depend on the value of the second virial coefficient. By mapping the HCAY and AO fluids onto an equivalent square-well fluid of appropriate range at the critical point we show that the critical temperature as a function of the effective range is independent of the interaction potential, i.e., all curves fall in a master curve. Our findings are corroborated with recent experimental data for lysozyme proteins.

Perturbation theory for multipolar discrete fluids.

An analytical expression for the Helmholtz free energy of discrete multipolar potentials as a function of density, temperature, and intermolecular parameters is obtained as an extension of the multipolar square-well perturbation theory [A. L. Benavides, Y. Guevara, and F. del Río, Physica A 202, 420 (1994)]. The presented procedure is suitable for the description of a more general intermolecular potential model taking into account the overlap and dispersion forces through a discrete potential represented by a sequence of square-shoulders and wells, as well as electrostatic interactions. The main advantage of this approach is that since the Helmholtz free energy is given as an explicit expression in terms of the intermolecular parameters characterizing the interaction, the properties of interest can be easily obtained through usual thermodynamic relations. Besides, since a great variety of discretized potentials can be used with this equation of state, its applicability is very vast. By varying the intermolecular parameters, some illustrative cases are considered, and their phase diagrams are tested against available simulation data. It is found that this theoretical approach is able to reproduce qualitatively and quantitatively well the vapor-liquid equilibrium of the chosen potentials with different multipole moment of varied strengths, except in the critical region.

Statistical thermodynamics of fluids with both dipole and quadrupole moments.

New Gibbs ensemble simulation data for a polar fluid modeled by a square-well potential plus dipole-dipole, dipole-quadrupole, and quadrupole-quadrupole interactions are presented. This simulation data is used in order to assess the applicability of the multipolar square-well perturbation theory [A. L. Benavides, Y. Guevara, and F. del Río, Physica A 202, 420 (1994)] to systems where more than one term in the multipole expansion is relevant. It is found that this theory is able to reproduce qualitatively well the vapor-liquid phase diagram for different multipolar moment strengths, corresponding to typical values of real molecules, except in the critical region. Hence, this theory is used to model the behavior of substances with multiple chemical bonds such as carbon monoxide and nitrous oxide and we found that with a suitable choice of the values of the intermolecular parameters, the vapor-liquid equilibrium of these species is adequately estimated.