Theory of Transient Localization, Activated Dynamics, and a Macromolecular Glass Transition in Ring Polymer Liquids

We construct a segmental scale force level theory for the center-of-mass diffusion constant and corresponding relaxation time for globally compact unconcatenated ring polymer solutions and melts (degree of polymerization N). The approach is based on slowly decaying macromolecular scale intermolecular force dynamic correlations as the origin of their unusual dynamics. Unentangled Rouse, weakly caged, and activated regimes are predicted. The barrier of the activated regime scales linearly with N and as a power law of concentration, which drives a kinetic glass transition on the radius-of-gyration scale. The values of N at the two dynamic crossovers (Rouse to weakly caged, weakly caged to activated) are proportional, with nonuniversality entering mainly via macromolecular volume fraction and dimensionless compressibility. Quantitative comparisons with simulation data reveal good agreement. Aspects of intermediate time dynamics are analyzed, and predictions are made for the conditions required to observe a macromolecular glass transition in the laboratory and on the computer.