Correction of Doi-Edwards' Green function for a chain in a harmonic potential and its implication for the stress-optic rule

Abstract

We provide a corrected Green's function for a polymer chain trapped in a two-dimensional anisotropic harmonic potential with a fixed boundary condition. This Green's function is a modified version of what Doi and Edwards first derived to describe the polymer chain confined in the tube-like domain of surrounding entangled polymers [J. Chem. Soc. Farad. Trans. II 74 (1978) 1802]. In contradiction to the results found by Ianniruberto and Marrucci (IM) when applying the Doi-Edwards Green function [J. Non-Newtonian Fluid Mech. 79 (1998) 225], we find that the stress-optical rule is violated for any tube potential either circular or elliptic if the corrected Green's function is used. The violation is due to the presence of the virtual springs to confine the chain in the tube rather than the anisotropy of the confinement potential. On the other hand, Doi and Edwards used their Green's function only for estimation of the monomer density along the primitive path where we find just a small correction. Since they did not use it for rheological calculations, the stress-optic rule appears to be safe for the Doi-Edwards model.