Scaling Laws for the Conformation and Viscosity of Ring Polymers in the Crossover Region around M_e 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 (M_w) from sub-Rouse (M_w < M_e) to reptation (M_w ∼ 10 M_e), where M_e 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 D_G as a function of PEO M_w 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 M_w.