Journal of Chemical Physics, Vol.104, No.2, 758-766, 1996
Dynamics of Chains in Excluded-Volume Conditions - Frequency-Dependent Viscosity CT Regular Star Chains
A theoretical treatment based on the Rouse-Zimm scheme is formulated to compute the relaxation times of an isolated elastic polymer chain with intramolecular interactions mimicking the excluded volume conditions. From these relaxation times, the intrinsic viscosity and the frequency-dependent viscosity of linear and regular star-branched chains have been computed. The conformational averages needed in the calculations are evaluated through a Monte Carlo sampling, to avoid any assumption on the distribution function of intramolecular distances. We observe an interesting curvature in the plots of the viscoelastic moduli G’ and G " against the frequency, which seems to be due to excluded volume interactions. Finally, the calculation and shape of the stress correlation function is discussed in terms of the constraining effects imposed by excluded volume in the vicinity of the branching point.
Keywords:FLUCTUATING HYDRODYNAMIC INTERACTIONS;RENORMALIZATION-GROUP CALCULATION;DILUTE POLYMER-SOLUTIONS;BROWNIAN DYNAMICS;GOOD-SOLVENT;MONTE-CARLO;VISCOMETRIC FUNCTIONS;DIMENSIONS;RELAXATION;SIMULATION