Fluctuation Effects in Semiflexible Diblock Copolymers

Shifan Mao; Quinn MacPherson; Andrew J Spakowitz

doi:10.1021/acsmacrolett.7b00638

Fluctuation Effects in Semiflexible Diblock Copolymers

ACS Macro Lett. 2018 Jan 16;7(1):59-64. doi: 10.1021/acsmacrolett.7b00638. Epub 2017 Dec 19.

Authors

Shifan Mao¹, Quinn MacPherson², Andrew J Spakowitz³

Affiliations

¹ Department of Chemical Engineering, ‡Department of Physics, §Department of Materials Science and Engineering, ∥Department of Applied Physics, and ⊥Biophysics Program, Stanford University, Stanford, California 94305, United States.
² Department of Chemical Engineering, Department of Physics, §Department of Materials Science and Engineering, ∥Department of Applied Physics, and ⊥Biophysics Program, Stanford University, Stanford, California 94305, United States.
³ Department of Chemical Engineering, Department of Physics, Department of Materials Science and Engineering, ∥Department of Applied Physics, and ⊥Biophysics Program, Stanford University, Stanford, California 94305, United States.

PMID: 35610917
DOI: 10.1021/acsmacrolett.7b00638

Abstract

We present a simulation study of the equilibrium thermodynamic behavior of semiflexible diblock copolymer melts. Using discretized wormlike chains and field-theoretic Monte Carlo, we find that concentration fluctuations play a critical role in controlling phase transitions of semiflexible diblock copolymers. Polymer flexibility and aspect ratio control the order-disorder transition Flory-Huggins parameter χ_ODTN. For polymers with low aspect ratios, fluctuations strongly elevate the phase transition χ_ODTN at finite molecular weights. For high aspect-ratio polymers, chain semiflexibility decreases the phase transition χ_ODTN. We find that the simulated phase behavior agrees well with our recently developed fluctuation theory based on wormlike chain configurations and a one-loop treatment of concentration fluctuations.