Activation Volumes for Solid-Solid Transformations in Nanocrystals

The transition between four- and six-coordinate structures in CdSe nanocrystals displays simple transition kinetics as compared with the extended solid, and we determined activation volumes from the pressure dependence of the relaxation times. Our measurements indicate that the transformation takes place by a nucleation mechanism and place strong constraints on the type of microscopic motions that lead to the transformation. The type of analysis presented here is difficult for extended solids, which transform by complicated kinetics and involve ill-defined domain volumes. Solids patterned on the nanoscale may prove to be powerful models for the general study of structural transitions in small systems, as well as in extended solids.