Nonequilibrium statistics of flexible macromolecules in dilute solutions. II. Macromolecular extension and comparison with nonequilibrium Brownian dynamics

Abstract

We derive an exact nonequilibrium expression for the probability density of the scalar extension of an arbitrary section of a Rouse chain in dilute solution. We use this new result to assess the accuracy of a new non-equilibrium Brownian dynamics (NEBD) computer simulation method for macromolecular fluids. The NEBD method allows the examination of systems which, because of their complexity, are intractable to analytical methods. Comparison of simulation results for Rouse chains in shear flow with analytical results for the distribution of the end-to-end distance and the distribution of individual chain segment extensions shows that NEBD does indeed produce reliable results.