Chain Confinement and Anomalous Diffusion in the Cross over Regime between Rouse and Reptation

Abstract

By neutron spin echo (NSE) and pulsed field gradient (PFG) NMR, we study the dynamics of a polyethylene-oxide melt (PEO) with a molecular weight in the transition regime between Rouse and reptation dynamics. We analyze the data with a Rouse mode analysis allowing for reduced long wavelength Rouse modes amplitudes. For short times, subdiffusive center-of-mass mean square displacement ⟨r_com²(t)⟩ was allowed. This approach captures the NSE data well and provides accurate information on the topological constraints in a chain length regime, where the tube model is inapplicable. As predicted by reptation for the polymer ⟨r_com²(t)⟩, we experimentally found the subdiffusive regime with an exponent close to $\mu =\frac{1}{2}$, which, however, crosses over to Fickian diffusion not at the Rouse time, but at a later time, when the ⟨r_com²(t)⟩ has covered a distance related to the tube diameter.