(606a) Thermodynamics and Kinetics of the Self-Assembly of Multiblock Oligomers

Macromolecules can be tailored to create multi-block molecules that vary not only in size and chemical composition but also in shape, rigidity, and branching topology. A key challenge that such boundless possibilities present to modelers is the ability to predict the assembling patterns of novel building blocks and to elucidate how microscopic order arises and be controlled. Overcoming such challenges will allow us to potentially identify phases with desirable structures and physical, electronic, catalytic or mechanical properties for emerging applications.

I will describe our modeling work on the phase behavior of multiblock macromolecules, i.e., molecules consisting of two or three chemical block types connected in such that are able to form complex mesophases with domains interspersing or percolating in all directions. I will show examples of systems that combine solid-like domains with liquid-like domains, which can be used, e.g., as dual electron/ionic conducting materials. Our results are filling some of the gaps in the rich phase behavior and the ionic conducting properties that have been mapped experimentally by collaborators. Concurrently, I will also describe some of the newer methodological variants developed in our group that use pattern-recognition order parameters to simulate free energies and to track the kinetic pathways by which the systems of interest undergo disorder-to-order transitions. Finally, I will outline some outstanding challenges pertaining the coarse-graining and inverse coarse-graining of multiblock oligomers.