Equilibrium sizes and formation energies of small and large Lennard-Jones clusters from molecular dynamics: A consistent comparison to Monte Carlo simulations and density functional theories

摘要

We have performed molecular dynamics simulations of Lennard-Jones argon clusters in equilibrium with a surrounding vapor and combined them with simulations of nucleation events in supersaturated vapor to investigate the dependence of critical cluster size on the vapor density in the cluster size range of 20-300 atoms. The simulations are performed at reduced temperature T-'=0.662, which with the parameter values of Lennard-Jones argon corresponds to 80 K. We obtain bulk equilibrium values by simulating a planar liquid-vapor interface. In the studied cluster size range, we find a linear relation between critical size Delta N-* and Delta mu(-3), where Delta mu is the chemical potential difference between supersaturated vapor and saturated vapor, but the slope of the line is not given by the Kelvin relation of classical nucleation theory. With this relation, along with the known formation energy of the small critical cluster of the nucleation simulations, we proceed to calculate the formation energies for larger critical sizes by integrating the nucleation theorem. We compare the molecular dynamics results to results from Monte Carlo simulations and both perturbative density functional theory and square gradient theory calculations. We find that the molecular dynamics results are in excellent agreement with the density functional and square gradient values. However, the Monte Carlo critical sizes and formation energies are somewhat lower than the molecular dynamics ones.