Micro-structural Change During Nucleation: From Nucleus To Bicontinuous Morphology

Although the microstructure of coexistence phase provides direct insights of the nucleation mechanism and their change is substantial in the phase transition, their study is limited due to the lack of suitable tools capturing the thermodynamically unstable transient states. We resolve this problem in computational study by introducing a generalized canonical ensemble simulation and investigate the morphological change of the nucleus during the water evaporation and condensation. We find that at very low pressure, where the transition is first order, classical nucleation theory holds approximately. A main nucleus is formed in the supersaturation near spinodal, and the overall shape of the nucleus is finite and compact. On increasing the pressure of the system, more nuclei are formed even before spinodal. They merge into a larger nuclei with a smaller free energy penalty to form ramified shapes. We suggest order parameters to describe the extent of fluctuation, and their relation to the free energy profile.