Anomalous Diffusion of a Polymer Chain in an Unentangled Melt

Contrary to common belief, hydrodynamic interactions in polymer melts are not screened beyond the monomer length and are important in transient regimes. We show that viscoelastic hydrodynamic interactions (VHIs) lead to anomalous dynamics of a tagged chain in an unentangled melt at t < t(N), the Rouse time. The center-of-mass (c.m.) mean-square displacement is enhanced by a large factor increasing with chain length. We develop a theory of VHI-controlled chain dynamics yielding a negative c.m. velocity autocorrelation function which agrees with our molecular dynamics simulations without any fitting parameter. It is also shown that Langevin friction strongly affects the short-t c.m. dynamics, also captured by our theory. The transient VHI effects thus provide the dominant contribution to the subdiffusive c.m. motion universally observed in simulations and experiments.