Mapping and Reverse-Mapping of the Morphologies for a Molecular Understanding of the Self-Assembly of Fluorinated Block Copolymers

A multiscale computational approach employing quantum mechanical, atomistic, and coarse-grained simulations has been adapted to reveal the self-assembly patterns of a styrene-co-fluorinated acrylate oligomer. Mesoscopic morphologies were determined using the dissipative particle dynamics method and were found to change from spherical micelles to hexagonal cylinders and lamella with increasing oligomer concentration. Quantum mechanics calculations were performed at the MP2/6-31(d) level of theory on the subsegments constituting the co-oligomer as well as on the shortest oligomer chain to determine the intermolecular interactions leading to the observed morphologies and self-assembly behavior. Atoms-in-molecules theory was employed to understand the nature of the noncovalent interactions between the styrene rings and between the fluorinated segments. A proportionality relation between the solubility parameters determined by the atomistic simulations and density functional theory-based reactivity descriptors such as global and local hardness is revealed.