Localization of chain dynamics in entangled polymer melts

The dynamics of polymer melts in both the unentangled and entangled regimes is described by a Langevin equation for the correlated motion of a group of chains, interacting through both intra- and inter-molecular potentials. Entanglements are represented by an intermolecular monomer-monomer confining potential that has no effect on short chains, while interpolymer interactions, responsible for correlated motion and subdiffusive center-of- mass dynamics, are represented by an intermolecular center-of- mass potential derived from the Ornstein-Zernike equation. This potential ensures that the liquid of phantom chains reproduces the compressibility and free energy of the real samples. For polyethylene melts the calculated dynamic structure factor is found to be in quantitative agreement with neutron spin echo experiments of polyethylene melts with chain lengths that span both the unentangled and the entangled regimes. The theory shows a progressive localization of the cooperative chain dynamics at the crossover from the unentangled to the entangled regime, in the spirit of the reptation model.