Liquid-Like States in Micelle-Forming Diblock Copolymer Melts.

Large cell self-consistent field theory (SCFT) solutions for a neat, micelle-forming diblock copolymer melt, initialized using the structure of a Lennard-Jones fluid, reveal the existence of a vast number of liquid-like states, with free energies of order 10 -3 k B T per chain higher than the body-centered cubic (bcc) state near the order-disorder transition (ODT). Computation of the structure factor for these liquids at temperatures below the ODT indicates that their intermicellar distance is slightly swollen compared to bcc. In addition to providing a mean-field picture of the disordered micellar state, the number of liquid-like states and their near-degeneracy with the equilibrium bcc morphology suggest that self-assembly of micelle-forming diblock copolymers navigates a rugged free energy landscape with many local minima. This picture provides a basis for the anomalously slow ordering kinetics of particle-forming diblock copolymer melts observed in experiments.