Free energy surface of two-step nucleation

Abstract

We test the theoretical free energy surface (FES) for two-step nucleation (TSN) proposed by Iwamatsu [J. Chem. Phys. 134, 164508 (2011)] by comparing the predictions of the theory to numerical results for the FES recently reported from Monte Carlo simulations of TSN in a simple lattice system [James, et al., J. Chem. Phys. 150, 074501 (2019)]. No adjustable parameters are used to make this comparison. That is, all the parameters of the theory are evaluated directly for the model system, yielding a predicted FES which we then compare to the FES obtained from simulations. We find that the theoretical FES successfully predicts the numerically-evaluated FES over a range of thermodynamic conditions that spans distinct regimes of behavior associated with TSN. All the qualitative features of the FES are captured by the theory and the quantitative comparison is also very good. Our results demonstrate that Iwamatsu's extension of classical nucleation theory provides an excellent framework for understanding the thermodynamics of TSN.

15 pages, 15 figures

References in corpus (4)

• Crystal Nucleation in Liquids: Open Questions and Future Challenges in Molecular Dynamics Simulations
• How crystals form: A theory of nucleation pathways
• Homogeneous ice nucleation evaluated for several water models
• Nucleation in aqueous NaCl solutions shifts from 1-step to 2-step mechanism on crossing the spinodal

Cited by in corpus (2)

• The Influence on Crystal Nucleation of an Order-Disorder Transition among the Subcritical Clusters
• Kinetic phase diagram for two-step nucleation in colloid-polymer mixtures