Nucleation and Growth in Structural Transformations of Nanocrystals

Using transition path sampling computer simulations, we reveal the nucleation mechanism of a pressure-induced structural transformation in CdSe nanocrystals. Consistent with experiments, the thermodynamic transition pressure of the transformation increases with decreasing crystal size. Through transition state analysis, we identify the critical nuclei and characterize them by calculating activation enthalpies and volumes. Our simulations reproduce the trends with crystal size observed in experiments. This result supports the observed transformation mechanism, which consists of nucleation on the crystal surface and growth by sliding of parallel crystal planes.