On the role of metastable intermediate states in the homogeneous nucleation of solids from solution
James F. Lutsko, "On the role of metastable intermediate states in the homogeneous nucleation of solids from solution", Adv. Chem. Phys., 151, 137 (2012) http://jimlutsko.github.io/files/Lutsko_AdvChemPhys_2011.pdf
The role of metastable liquid phases in vapor-crystal nucleation is studied using Density Functional Theory(DFT). The model gives a semi-quantitatively accurate description of both the vapor-liquid-solid phase diagram for both simple fluids (Lennard-Jones interactions) and of the low-density/high-density/crystal phase diagram for model globular proteins (ten Wolde-Frenkel interaction). The density profile is characterized by two local order parameters, the average density and the crystallinity. The bulk free energy model is supplemented by squared-derivative terms in these order parameters to account for inhomogeneities thus producing a model similar in spirit to phase-field theory. It is shown that for both interaction models, the vapor-crystal part of the phase-diagram can be separated into regions for which metastable liquid phases are more or less stable than the vapor, but always less stable than the solid. The former case allows for the possibility of double nucleation whereby liquid droplets nucleate from the vapor followed by a separate nucleation of the solid phase within the liquid droplets. Whether or not this actually occurs depends on the relative free energy barriers for vapor-solid and vapor-liquid nucleation and it is shown that for simple fluids, double nucleation is indeed favored at sufficiently large supersaturation. Finally, by studying the minimum free energy path from the vapor to the solid, the separate possibility of transient nucleation.