Crossover between activated reptation and arm retraction mechanisms in entangled rod-coil block copolymers

Using a coarse-grained slip-spring model, the dynamics of rod-coil block copolymers is explored over a wide parameter space to fully capture the crossover between the short rod (activated reptation) and long rod (arm retraction) limits. An analytical, closed-form expression for curvilinear diffusion by activated reptation was derived by separating the drag into individual components for the rod and coil block. Curvilinear diffusion in the intermediate rod regime, where both mechanisms are important, was then found to be faster than predicted when both mechanisms are independently combined. The discrepancy in the crossover regime arises because the rod-coil copolymer's exploration of space is not accurately described by either a coil homopolymer (assumed by activated reptation) or a rod homopolymer (assumed by arm retraction). This effect is explored by tracking the rod orientation as the polymer reptates, confirming that the polymer reptates along a path that becomes more rodlike as the rod fraction is increased. Thus, activated reptation under-predicts diffusion because the rod can choose reptation paths that are more extended than the coil homopolymer by renewal of the entanglement tube from the ends. Arm retraction under-predicts diffusion because minor rotations of the rod allow some motion before full retractions of the coil block. Finally, more familiar 3-dimensional center-of-mass diffusion measurements are related to the curvilinear diffusion analysis because the ratio of these two quantities varies smoothly between the coil and rod homopolymer limits as the reptation path becomes more extended.