Kinetic phase diagram for two-step nucleation in colloid-polymer mixtures
arXiv:2504.06922 · doi:10.1063/5.0251560
Abstract
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.
18 pages
References in corpus (22)
- Robust Structural Identification via Polyhedral Template Matching
- Crystal Nucleation in Liquids: Open Questions and Future Challenges in Molecular Dynamics Simulations
- Nonequilibrium free-energy calculation of solids using LAMMPS
- Crystal nucleation of hard spheres using molecular dynamics, umbrella sampling and forward flux sampling: A comparison of simulation techniques
- How crystals form: A theory of nucleation pathways
- A parameter-free, solid-angle based, nearest-neighbor algorithm
- Evidence for out-of-equilibrium crystal nucleation in suspensions of oppositely charged colloids
- Interfacial Free Energy as the Key to the Pressure-Induced Deceleration of Ice Nucleation
- Crystallization and gelation in colloidal systems with short-ranged attractive interactions
- Limit of validity of Ostwald's rule of stages in a statistical mechanical model of crystallization
- Seeding Approach to nucleation in the NVT ensemble: the case of bubble cavitation in overstretched Lennard Jones fluids
- Phase transitions in fluctuations and their role in two-step nucleation
- Free-energy landscape of nucleation with an intermediate metastable phase studied using capillarity approximation
- Early-Stage Bifurcation of Crystallization in a Sphere
- Kinetic phase diagram for nucleation and growth of competing crystal polymorphs in charged colloidal suspensions
- Free energy surface of two-step nucleation
- Brute-force nucleation rates of hard spheres compared with rare-event methods and classical nucleation theory
- Variational Umbrella Seeding for Calculating Nucleation Barriers
- Finding the Differences: Classical Nucleation Perspective on Homogeneous Melting and Freezing of Hard Spheres
- The Influence on Crystal Nucleation of an Order-Disorder Transition among the Subcritical Clusters
- Revisiting Shooting Point Monte Carlo Methods for Transition Path Sampling
- Solid-liquid interfacial free energy from computer simulations: Challenges and recent advances