Computational Approaches for the Dynamics of Structure Formation in Self-Assembling Polymeric Materials

Polymeric materials can assemble into a multitude of intricate nanoscale morphologies whose free energy differs by only a fraction of the thermal energy per molecule. Such small free-energy differences pose a challenge for modeling and simulation but also offer exciting opportunities to direct the assembly of such materials into morphologies that do not correspond to those of equilibrium bulk structures. Over the past decade, significant progress has been achieved in our ability to guide their self-assembly through the use of confinement, topographical or chemical patterns, and electric fields. In contrast, approaches to guide self-assembly by tailoring the dynamics of structure formation have received less attention. This review discusses opportunities and challenges of recently developed computational strategies to predict the dynamics of self-assembly of polymeric materials on the basis of the underlying free-energy landscape.