Corrections to Scaling in the Hydrodynamic Properties of Dilute Polymer Solutions

We discuss the hydrodynamic radius $R_H$ of polymer chains in good solvent, and show that the leading order correction to the asymptotic law $R_H \propto N^\nu$ ($N$ degree of polymerization, $\nu \approx 0.59$) is an ``analytic'' term of order $N^{-(1 - \nu)}$, which is directly related to the discretization of the chain into a finite number of beads. This result is further corroborated by exact calculations for Gaussian chains, and extensive numerical simulations of different models of good--solvent chains, where we find a value of $1.591 \pm 0.007$ for the asymptotic universal ratio $R_G / R_H$, $R_G$ being the chain's gyration radius. For $\Theta$ chains the data apparently extrapolate to $R_G / R_H \approx 1.44$, which is different from the Gaussian value 1.5045, but in accordance with previous simulations. We also show that the experimentally observed deviations of the initial decay rate in dynamic light scattering from the asymptotic Benmouna--Akcasu value can partly be understood by similar arguments.