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Scaling Laws for the Conformation and Viscosity of Ring Polymers in the Crossover Region around Me from Detailed Molecular Dynamics Simulations.

We present results from detailed, atomistic molecular dynamics (MD) simulations of pure, strictly monodisperse linear and ring poly(ethylene oxide) (PEO) melts under equilibrium and nonequilibrium (shear flow) conditions. The systems examined span the regime of molecular weights (Mw) from sub-Rouse (Mw < Me) to reptation (Mw ∼ 10 Me), where Me denotes the characteristic entanglement molecular weight of linear PEO. For both PEO architectures (ring and linear), the predicted chain center-of-mass self-diffusion coefficients DG as a function of PEO Mw are in remarkable agreement with experimental data. From the flow simulations under shear, we have extracted and analyzed the zero-shear viscosity of ring and linear PEO melts as a function of Mw.