Stresses inside critical nuclei
The usual derivation of classical nucleation theory is inappropriate for crystal nucleation. In particular, it leads to a seriously flawed estimate of the pressure inside a critical nucleus. This has consequences for the prediction of possible metastable phases during the nucleation process. In this paper, we reanalyze the theory for crystal nucleation based on the thermodynamics of small crystals suspended in a liquid, due to Mullins (J. Chem. Phys. 1984, 81, 1436). As an illustration of the difference between the classical picture and the present approach, we consider a numerical study of crystal nucleation in binary mixtures of hard spherical colloids with a size ratio of 1:10. The stable crystal phase of this system can be either dense or expanded. We find that, in the vicinity of the solid-solid critical point where the crystallites are highly compressible, small crystal nuclei are less dense than large nuclei. This phenomenon cannot be accounted for by either classical nucleation theory or by the Gibbsian droplet model.