Falsity of the Rouse Mode Solution of the Rouse and Zimm Models

Abstract

The Rouse (J. Chem. Phys. 21, 1272 (1953)) and Zimm (J. Chem. Phys. 24}, 269 (1956)) treatments of the dynamics of a polymer chain are shown to contain a fundamental mathematical error, which causes them to lose the zero-relaxation-rate, whole-body rotation motions dominant in viscosity and dielectric relaxation. As a result, the oft-cited mode solutions for these models are qualitatively incorrect. Comparison with the Wilson-Decius-Cross treatment of vibrational modes of polyatomic molecules reveals qualitatively the correct form for the solutions to the Rouse model.