The optimized Rouse-Zimm theory of excluded volume effects on chain dynamics.
Based on the optimized Rouse-Zimm (ORZ) approximation to the Kirkwood diffusion equation, we investigate the effects of excluded volume interactions on the single chain dynamics. By incorporating the nonuniformly expanded moments of interbead distances into the expressions for the diffusion and structure matrices appearing in the ORZ diffusion equation, we obtain the general relaxation spectrum for flexible chains that is valid over the range from theta; solvents to good solvents. The present theory involves four parameters: the Kuhn statistical length b(0), the bead number N, the excluded volume parameter z, and the hydrodynamic interaction parameter h(*). These model parameters are determined from structural data of polymers with the aid of the quasi-two-parameter theory. The set of relaxation times of ORZ normal modes calculated with these bead-and-spring model parameters enables the theoretical prediction of various frictional and dynamical properties of polymers within a unified framework. The present ORZ theory generalizes the Ptitsyn-Eizner-type approaches by incorporating the nonuniform chain expansion effect into the structure matrix as well as the diffusion matrix.
Kim
Ji-Hyun
JH
School of Chemistry and Molecular Engineering, Seoul National University, Seoul 151-747, South Korea.
Lee
Sangyoub
S