J Chem Phys. 2015 Mar 07;142(9):094501. doi: 10.1063/1.4913592.
The Journal of chemical physics
T Philippe
PMID: 25747088 DOI: 10.1063/1.4913592
Nucleation is studied in incompressible ternary fluids by examining the topology of the overall landscape of the energy surface. Minimum free energy paths for nucleation (MFEPs) of a single nucleus in an infinite matrix are computed with the string method in the framework of the continuum theory of nucleation for the regular solution. Properties of the critical nucleus are compared with the predictions of the classical nucleation theory. MFEPs are found to exhibit complex nucleation pathways with non-monotonic variations of compositions in the interfacial region, specifically adsorption of a component. In the symmetric regular solution, the minority component is found to segregate at the interface during nucleation with a concomitant depletion of the nucleus core, resulting in unpredicted partition of the non-selective component. Despite increasing the gradient energy, such inhomogeneity in composition is shown to lower the nucleation barrier.
