Mechanism of two-step vapour–crystal nucleation in a pore

Abstract

We present a numerical study of the effect of hemispherical pores on the nucleation of Lennard–Jones crystals from the vapour phase. As predicted by Page and Sear, there is a narrow range of pore radii, where vapour–liquid nucleation can become a two-step process. A similar observation was made for different pore geometries by Giacomello et al. We find that the maximum nucleation rate depends on both the size and the adsorption strength of the pore. Moreover, a poe can be more effective than a planar wall with the same strength of attraction. Pore-induced vapour–liquid nucleation turns out to be the rate-limiting step for crystal nucleation. This implies that crystal nucleation can be enhanced by a judicious choice of the wetting properties of a microporous nucleating agent.