Complex Interactions with the Surroundings Dictate a Tagged Chain’s Dynamics in Unentangled Polymer Melts

Abstract

For more than half a century the theoretical landscape for single chain dynamics for dense polymeric solutions and melts below the entanglement threshold has been dominated by the Rouse model for independent phantom chains, supported by ideas of hydrodynamic screening. There exists, however, a large body of literature from experiments, Monte Carlo, and molecular dynamics simulations on the deviations from the Rouse behavior for unentangled homopolymer melts, showcased mostly in the subdiffusive behavior of center-of-mass of tagged chains at intermediate times, with the subdiffusion exponent reported in the range 0.75–0.85. The influence of the surrounding chains of length Ns on the motion of a single tagged chain of length N is a key test, by which, through high-precision numerical simulation of unentangled melts, we show that the Rouse model fails. Our central results are that at intermediate times the tagged chain’s center-of-mass moves subdiffusively, ⟨Δr2cm⟩ ∝ tα with subdiffusion exponent α = 0.87 ± ...