Phase diagram of symmetric binary mixtures at equimolar and non-equimolar concentrations: a systematic investigation

Abstract

We consider symmetric binary mixtures consisting of spherical particles with equal diameters interacting via a hard-core plus attractive tail potential with strengths epsilon_{ij}, i,j=1,2, such that epsilon_{11} = epsilon_{22} > epsilon_{12}. The phase diagram of the system at all densities and concentrations is investigated as a function of the unlike-to-like interaction ratio delta = epsilon_{12}/epsilon_{11} by means of the hierarchical reference theory (HRT). The results are related to those of previous investigations performed at equimolar concentration, as well as to the topology of the mean-field critical lines. As delta is increased in the interval 0 < delta < 1, we find first a regime where the phase diagram at equal species concentration displays a tricritical point, then one where both a tricritical and a liquid-vapor critical point are present. We did not find any clear evidence of the critical endpoint topology predicted by mean-field theory as delta approaches 1, at least up to delta=0.8, which is the largest value of delta investigated here. Particular attention was paid to the description of the critical-plus-tricritical point regime in the whole density-concentration plane. In this situation, the phase diagram shows, in a certain temperature interval, a coexistence region that encloses an island of homogeneous, one-phase fluid.