Free energy calculations along entropic pathways: II. Droplet nucleation in binary mixtures (2108.10377v1)

Abstract: Using molecular simulation, we study the nucleation of liquid droplets from binary mixtures and determine the free energy of nucleation along entropic pathways. To this aim, we develop the $\mu_1 \mu_2 VT-S$ method, based on the grand-canonical ensemble modeling the binary mixture, and use the entropy of the system $S$ as the reaction coordinate to drive the formation of the liquid droplet. This approach builds on the advantages of the grand-canonical ensemble, which allows for the direct calculation of the entropy of the system and lets the composition of the system free to vary throughout the nucleation process. Starting from a metastable supersaturated vapor, we are able to form a liquid droplet by gradually decreasing the value of $S$, through a series of umbrella sampling simulations, until a liquid droplet of a critical size has formed. The $\mu_1 \mu_2 VT-S$ method also allows us to calculate the free energy barrier associated with the nucleation process, to shed light on the relation between supersaturation and free energy of nucleation, and to analyze the interplay between the size of the droplet and its composition during the nucleation process.