Application of the Kirkwood theory of transport in polymer solutions to rigid assemblies of beads

Abstract

The Kirkwood general theory of irreversible processes in polymer solutions is reformulated to give correct translational and rotatory diffusion coefficients for highly symmetric, rigid molecules which may be represented by rigid assemblies of beads. This provides an elementary description of the physical meaning of the Kirkwood approximation, and gives simple criteria to judge whether Kirkwood's incorrect formulas are or are not exactly valid for a given system. Following the formulation presented here, translational and rotatory diffusion coefficients of rigid rods and rigid rings are also evaluated.