Breakdown of Classical Nucleation Theory near Isostructural Phase Transitions
- 15 October 2004
- journal article
- research article
- Published by American Physical Society (APS) in Physical Review Letters
- Vol. 93 (16), 166105
- https://doi.org/10.1103/physrevlett.93.166105
Abstract
We report simulations of crystal nucleation in binary mixtures of hard spherical colloids with a size ratio of . 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.
This publication has 21 references indexed in Scilit:
- Phase diagram of highly asymmetric binary hard-sphere mixturesPhysical Review E, 1999
- Phase Behavior and Structure of Binary Hard-Sphere MixturesPhysical Review Letters, 1998
- Crystal nucleation in the presence of a metastable critical pointThe Journal of Chemical Physics, 1998
- Enhancement of Protein Crystal Nucleation by Critical Density FluctuationsScience, 1997
- bcc Symmetry in the Crystal-Melt Interface of Lennard-Jones Fluids Examined through Density Functional TheoryPhysical Review Letters, 1996
- Numerical Evidence for bcc Ordering at the Surface of a Critical fcc NucleusPhysical Review Letters, 1995
- Density-functional theory of solid-to-solid isostructural transitionsJournal of Physics: Condensed Matter, 1994
- van der Waals theory for solidsPhysical Review E, 1994
- Prediction of an expanded-to-condensed transition in colloidal crystalsPhysical Review Letters, 1994
- Studien über die Bildung und Umwandlung fester KörperZeitschrift für Physikalische Chemie, 1897