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

TL;DR

This paper introduces the $VT-S$ simulation method using entropy as a reaction coordinate to accurately study vapor-liquid nucleation, demonstrating its effectiveness for atomic and molecular systems and providing new insights into droplet formation.

Contribution

The paper develops and validates the $VT-S$ method combining grand-canonical ensemble and umbrella sampling, enabling direct entropy evaluation for nucleation studies in atomic and molecular fluids.

Findings

The $VT-S$ method correctly predicts free energy barriers and critical droplet sizes.

Application to argon confirms consistency with classical nucleation theory.

Versatile transferability demonstrated through molecular systems like N2 and CO2.

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 $\mu VT-S$ 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 $\mu VT-S$ 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 classical nucleation theory and to previous simulation results. In addition, it provides insight into the relation between entropy and droplet formation throughout this process. An additional advantage of the $\mu VT-S$ approach is its direct transferability to molecular systems, since it uses the entropy of the system as the reaction coordinate. Applications of the $\mu VT-S$ simulation method to $N_2$ and $CO_2$ are presented and discussed in this work, showing the versatility of the $\mu VT-S$ approach.