Finite-size effects in simulations of nucleation.

ABSTRACT

We investigate the importance of finite-size effects in simulations of nucleation processes. Most molecular dynamics simulations of first order phase transitions, such as vapor-liquid nucleation, are performed in the canonical NVT ensemble where, owing to the fixed total number of molecules N, the growth of the new phase causes the depletion of the metastable phase. This effect may lead to significant errors in the simulation and even to the impossibility of observing nucleation in a small finite system. We present a theory to estimate the system size beyond which these finite-size effects are expected to be negligible. This optimization saves valuable calculation time and can extend the range of supersaturations and rates attainable by simulations by several orders of magnitude. Our results are applicable to diverse situations, such as crystallization, capillary condensation, or the melting of nanoclusters.