Kinetic phase diagram for two-step nucleation in colloid–polymer mixtures

Two-step crystallization via a metastable intermediate phase is often regarded as a non-classical process that lies beyond the framework of classical nucleation theory (CNT). In this work, we investigate two-step crystallization in colloid-polymer mixtures via an intermediate liquid phase. Using CNT-based seeding simulations, we construct a kinetic phase diagram that identifies regions of phase space where the critical nucleus is either liquid or crystalline. These predictions are validated using transition path sampling simulations at nine different relevant state points. When the critical nucleus is liquid, crystallization occurs stochastically during the growth phase, whereas for a crystalline critical nucleus, the crystallization process happens pre-critically at a fixed nucleus size. We conclude that CNT-based kinetic phase diagrams are a powerful tool for understanding and predicting "non-classical" crystal nucleation mechanisms.