Translational Diffusion of Polymer Chains with Excluded Volume and Hydrodynamic Interactions by Brownian Dynamics Simulation

Abstract

Within Kirkwood theory, we study the translational diffusion coefficient of a single polymer chain in dilute solution, and focus on the small difference between the short--time Kirkwood value $D^{(K)}$ and the asymptotic long--time value $D$. We calculate this correction term by highly accurate large--scale Brownian Dynamics simulations, and show that it is in perfect agreement with the rigorous variational result $D < D^{(K)}$, and with Fixman's Green--Kubo formula, which is re--derived. This resolves the puzzle posed by earlier numerical results (Rey {\em et al.}, Macromolecules 24, 4666 (1991)), which rather seemed to indicate $D > D^{(K)}$; the older data are shown to have insufficient statistical accuracy to resolve this question. We then discuss the Green--Kubo integrand in some detail. This function behaves very differently for pre--averaged vs. fluctuating hydrodynamics, as shown for the initial value by analytical considerations corroborated by numerical results. We also present further numerical data on the chain's statics and dynamics.