Competition between clustering and phase separation in binary mixtures containing SALR particles

We investigate by Monte Carlo simulations a mixture of particles with competing interactions (hard-sphere two-Yukawa, HSTY) and hard spheres (HS), with same diameters σ and a square-well (SW) cross attraction. In a recent study [G. Munaò et al., J. Phys. Chem. B, 2022, 126, 2027–2039], we have analysed situations—in terms of relative concentration and attraction strength—where HS promote the formation of clusters involving particles of both species under thermodynamic conditions that would not allow for clustering of the pure HSTY fluid. Here, we focus on the role played by the range of cross attraction in determining the equilibrium structure of the mixture, starting from a homogeneous low-density state. When the width of the well exceeds approximately σ, clustering takes place in the system, with aggregates characterised by various sizes and shapes. Only for low HSTY concentrations (less than 10%) a single big cluster appears, anticipating the behaviour observed for a wider well, around 1.2σ. In the latter case, a spherical cluster encompassing almost all particles is the stable structure at equilibrium. We interpret this outcome as a macrophase, liquid–vapour separation where the spherical cluster is just the form taken at low density by the liquid phase inside the vapour phase: indeed, when the density takes larger values, periodic boundary conditions select liquid–vapour interfaces with other non-spherical shapes, similarly as found for a finite sample of simple fluid going through the liquid–vapour coexistence region. For still higher densities we document the existence of a solid phase characterized by the alternation of bilayers filled with particles of one species and bilayers of the other species, giving the solid a peculiar wafer structure.