Transition Pathways for Exchange and Fission in Diblock Copolymer Micelles

Surfactant and polymer-based micelles are ubiquitous in both nature and industry. They exist naturally within our cells and are leveraged across many fields and applications, such as drug delivery and viscosity modification of oils and consumer products. Chain expulsion/insertion and micelle fission/fusion are the two most fundamental processes governing micelle aggregation and dynamics. The exact pathways for these processes, and how dominant they are in micelle formation and destruction, has long been debated. Most experimental results of chain exchange have been evaluated in the context of the Halperin and Alexander mechanism, where the core block is assumed to collapse upon entering the corona, leading to a N^2/3 scaling of the free energy barrier. Recent experiments and simulations, however, have reported linear scaling in N, calling into question the validity of the budding-like mechanism. We evaluate both the exchange and fission problems from multiple perspectives by employing state-of-the art enhanced sampling techniques in molecular dynamics simulations, as well as using dynamic self-consistent field theory coupled with the string method. We analyze the minimum free energy transition pathways and energy barriers across different chain lengths and interaction strengths.