Vapor-to-droplet transition in a Lennard-Jones fluid: simulation study of nucleation barriers using the ghost field method

Abstract

We report a comprehensive Monte Carlo (MC) simulation study of the vapor-to-droplet transition in Lennard-Jones fluid confined to a spherical container with repulsive walls, which is a case study system to investigate homogeneous nucleation. The focus is made on the application of a modified version of the ghost field method (Vishnyakov, A.; Neimark, A. V. J. Chem. Phys. 2003, 119, 9755) to calculate the nucleation barrier. This method allows one to build up a continuous trajectory of equilibrium states stabilized by the ghost field potential, which connects a reference droplet with a reference vapor state. Two computation schemes are employed for free energy calculations, direct thermodynamic integration along the constructed trajectory and umbrella sampling. The nucleation barriers and the size dependence of the surface tension are reported for droplets containing from 260 to 2000 molecules. The MC simulation study is complemented by a review of the simulation methods applied to computing the nucleation barriers and a detailed analysis of the vapor-to-droplet transition by means of the classical nucleation theory.