INTRAMOLECULAR DIFFUSION-CONTROLLED REACTIONS IN POLYMERS IN THE OPTIMIZED ROUSE ZIMM APPROACH .1. THE EFFECTS OF CHAIN STIFFNESS, REACTIVE SITE POSITIONS, AND SITE NUMBERS

The Wilemski-Fixman approach to diffusion-controlled intramolecular reactions in polymer solutions is extended to the optimized Rouse-Zimm (ORZ) hierarchy of dynamic models. The effect of chain stiffness is treated by using the ORZ approximation of the freely rotating chain in the entire range between Gaussian chains and rods. For two reactive sites in the interior of the chain, the pure dynamic effect of the length of the lateral tails on the rate constant is considered and found to be dependent on the capture radius. The case of evenly spaced catalytic sites with a central reactive group is exactly solved and the results are compared with the simple hypothesis of the reaction additivity. © 1990, American Chemical Society. All rights reserved.