(74g) Unusual Crystallization Behavior Close to the Glass Transition

Using molecular simulation, we examine how the choice of crystallization conditions can impact the outcome of the process. Specifically, by carrying out the crystallization process close to the glass transition, we show how the nucleation free energy exhibits an unusual behavior and is found to increase as the temperature decreases and gets closer and closer to the glass transition. We interpret this finding as the result of the onset of a medium-range order, characterized by connected icosahedra, that is incompatible with the crystalline order, and leads to an increase in the height of the free energy barrier. We discuss applications of this approach to several systems.