Monte Carlo Simulations on Heterogeneous Nucleation I: The Point Where the Classical Theory Fails

We have performed Monte Carlo simulations of homogeneous and heterogeneous nucleations of Lennard–Jones argon clusters. We interpreted the simulation results using the major concept posing a difference between the homogeneous and heterogeneous classical nucleation theories, the contact parameter. Our results show that the concept describes the cluster–substrate interaction surprisingly well, even for very small molecular clusters. The use of the classical theory concept results in an underestimation of the heterogeneous nucleation rate by 2–3 orders of magnitude. The main contribution is induced by the failure of the classical theory of homogeneous nucleation to predict the energy involved in bringing one molecule from the vapor to the cluster for clusters containing less than approximately 15 molecules.

Keywords Heterogeneous nucleation, Monte Carlo simulations, argon