Influence of variable hydrodynamic interaction strength on the transport properties of coiled polymers.
We have computed the hydrodynamic radius Rh and intrinsic viscosity [eta] of a large number of random coil polymer models by path integration. We examine the effects of chain length, solvent quality, monomer size and shape, and chain stiffness on the approach of these transport properties to the limit of large molecular mass. For many of the models, we have also calculated the ensemble-averaged solvent velocity field in the vicinity of the coil as it moves with constant drift velocity under the action of an external force. Naive scaling arguments predict alpha=nu and beta=3(nu-1) , where alpha , beta , and nu are the exponents controlling the chain length behavior of Rh , [eta] , and Rg , respectively. We present evidence for a "draining crossover" that quantifies the slow convergence of the transport properties to their asymptotic scaling behavior. Indeed, the convergence is so slow that effective alpha and beta exponents rarely agree with the naive predictions at typical molecular masses. For the same chain models, Rg converges rapidly to its asymptotic behavior, indicating that the effect is not due to a crossover from theta to swollen behavior, as often stated. Solvent quality, monomer size, and chain stiffness all influence the draining crossover. Our results call into question the common practice of extracting metrical data, e.g., characteristic ratios, directly from polymer solution transport properties.
Mansfield
Marc L
ML
Department of Chemistry, Chemical Biology, and Biomedical Engineering, Stevens Institute of Technology, Hoboken, New Jersey 07030, USA. marc.mansfield@stevens.edu
Douglas
Jack F
JF
D055595:Mechanical Phenomena; D008958:Models, Molecular; D008968:Molecular Conformation; D011108:Polymers / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D013499:Surface Properties
D011108:Polymers; D012997:Solvents