Simulation of Dynamical Processes in Block Copolymer Micelles

Micellar solutions exhibit a "fast" dynamical process associated with single-molecular insertion and expulsion and a "slow" process associated with birth and death of entire micelles. We report an analysis of simulations of highly asymmetric "hairy" micelles that is designed to quantify rates of both types of process, and to elucidate mechanisms. By modeling diffusion of the micelle aggregation number on a well characterized free energy surface, we are able to calculate and compare relaxation for different possible mechanisms for the slow process, which would otherwise be computationally inaccessible. This method allows us to compare the rate for step-wise association and dissociation to the rate of the competing mechanism of micelle fission and fusion.