Free energy calculations along entropic pathways. I. Homogeneous vapor-liquid nucleation for atomic and molecular systems.

Abstract

Using the entropy S as a reaction coordinate, we determine the free energy barrier associated with the formation of a liquid droplet from a supersaturated vapor for atomic and molecular fluids. For this purpose, we develop the μVT-S simulation method that combines the advantages of the grand-canonical ensemble, that allows for a direct evaluation of the entropy, and of the umbrella sampling method, that is well suited to the study of an activated process like nucleation. Applying this approach to an atomic system such as Ar allows us to test the method. The results show that the μVT-S method gives the correct dependence on supersaturation of the height of the free energy barrier and of the size of the critical droplet, when compared to predictions from the classical nucleation theory and to previous simulation results. In addition, it provides insight into the relation between the entropy and droplet formation throughout this process. An additional advantage of the μVT-S approach is its direct transferability to molecular systems, since it uses the entropy of the system as the reaction coordinate. Applications of the μVT-S simulation method to N2 and CO2 are presented and discussed in this work, showing the versatility of the μVT-S approach.