Arrested states in colloidal fluids with competing interactions: A static replica study

Abstract

We present the first systematic application of the integral equation implementation of the replica method to the study of arrested states in fluids with microscopic competing interactions (short-range attractive and long-range repulsive, SALR), as exemplified by the prototype Lennard-Jones–Yukawa model. Using a wide set of potential parameters, we provide as many as 11 different phase diagrams on the density (ρ)–temperature (T) plane, embodying both the cluster-phase boundary, TC(ρ), and the locus below which arrest takes place, TD(ρ). We describe how the interplay between TC and TD—with the former falling on top of the other, or the other way around, depending on thermodynamic conditions and potential parameters—gives rise to a rich variety of non-ergodic states interspersed with ergodic ones, of which both the building blocks are clusters or single particles. In a few cases, we find that the TD locus does not extend all over the density range subtended by the TC envelope; under these conditions, the λ-line is within reach of the cluster fluid, with the ensuing possibility to develop ordered microphases. Whenever a comparison is possible, our predictions favorably agree with previous numerical results. Thereby, we demonstrate the reliability and effectiveness of our scheme to provide a unified theoretical framework for the study of arrested states in SALR fluids, irrespective of their nature.