Single Chain Expulsion from Diblock Copolymer Micelles with Dense Corona

Abstract

We use self-consistent field theory to investigate the free energy landscape for single-chain expulsion from a diblock copolymer micelle with a dense corona. Using the distance from the micelle center-of-mass to the hydrophilic-hydrophobic junction of the chain as the reaction coordinate, we compute the free energy landscape for chain exchange. Our results show that the expulsion free energy barrier scales linearly with both the hydrophobic block length and the solvent selectivity, consistent with recent experiments. To accurately resolve chain conformation, we introduce a second reaction coordinate: the distance between the junction and the free end of the hydrophobic block, and construct a two-dimensional free energy surface. Using the string method to identify the minimum energy path, we find that all pathways converge to a nearly degenerate reaction channel, irrespective of the initial path. Within this channel, the end-to-end distance of the hydrophobic block exhibits a broad distribution, yet the corresponding expulsion barriers remain nearly indistinguishable. Together, these findings establish a continuum-level theoretical foundation for understanding the hyperstretching mechanism and the transition state ensemble in micellar chain exchange.