Cross-Interaction Softness as a Route to Microphase Separation in Binary Colloidal Systems

Abstract: Understanding how interparticle interactions govern phase behavior is central to controlling self-organization in multicomponent soft-matter systems. In particular, the role of cross-interactions between unlike components remains insufficiently understood. Here, we systematically investigate how cross-interaction character controls phase behavior in binary mixtures of hard and soft particles using coarse-grained modeling, Reference Interaction Site Model (RISM) theory, and molecular dynamics simulations. Four representative systems are examined that differ only in whether interactions between unlike particles are bounded or hard-sphere. We show that penetrable (bounded) cross-interactions are both necessary and sufficient to induce microphase separation, even in the absence of attractive forces. Such systems exhibit dispersed states, macrophase separation, and microphase-separated morphologies characterized by finite-wavelength compositional ordering. In contrast, purely hard-sphere cross interactions suppress microphase separation entirely, despite strong local clustering. Comparison between theory and simulations reveals qualitative agreement in phase topology, while simulations additionally capture hierarchical and multiscale ordering near crossover regimes. These findings establish cross-interaction softness as a fundamental design principle for controlling phase behavior in multicomponent colloidal and soft-matter systems.