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Published July 18, 2023 | Supplemental Material
Journal Article Open

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.

Additional Information

© 2023 American Chemical Society. We thank Frank S. Bates, David C. Morse, Timothy P. Lodge, and Benjamin R. Magruder for useful discussions. K.D.D. acknowledges the gracious hospitality of the California Institute of Technology during portions of this work. Z.-G.W. acknowledges support by Hong Kong Quantum AI Lab, AIR@InnoHK of Hong Kong Government. Computational resources were provided by the Minnesota Supercomputing Institute. Author Contributions: CRediT: Kevin D. Dorfman conceptualization (supporting), data curation (lead), investigation (lead), methodology (equal), software (lead), writing-original draft (lead), writing-review & editing (equal); Zhen-Gang Wang conceptualization (lead), investigation (supporting), methodology (equal), writing-review & editing (equal). The authors declare no competing financial interest.

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August 22, 2023
October 20, 2023