Long-wavelength density fluctuations as nucleation precursors.

ABSTRACT

Recent theories of nucleation that go beyond classical nucleation theory predict that diffusion-limited nucleation of both liquid droplets and of crystals from a low-density vapor (or weak solution) begins with long-wavelength density fluctuations. This means that in the early stages of nucleation, "clusters" can have low density but large spatial extent, which is at odds with the classical picture of arbitrarily small clusters of the condensed phase. We present the results of kinetic Monte Carlo simulations using forward flux sampling to show that these predictions are confirmed, namely, that on average, nucleation begins in the presence of low-amplitude, but spatially extended density fluctuations thus confirming a significant prediction of the nonclassical theory.