Breakdown of classical nucleation theory near isostructural phase transitions.

We report simulations 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. We argue that the observed behavior is due to the surface stress of the crystal nuclei. The observed effect highlights a general deficiency of the most frequently used thermodynamic theories for crystal nucleation. Surface stress should lead to an experimentally observable expansion of crystal nuclei of colloids with short-ranged attraction and of globular proteins.