Past exam of the soft condensed matter course of the University of Cambridge / 2012 / Paper 1 / 3 / e / Solution

In a dilute solution, separate coils diffuse through solvent with long-ranged hydrodynamic coupling among their segments. The Zimm model gives whole-chain diffusionwhere $R_H$ is a hydrodynamic radius and ${\eta }_s$ the solvent viscosity. The coil continually changes shape while its centre of mass performs long-time Brownian motion; treating it as a rigid sphere is only a scaling analogy.

At high concentration, solvent-mediated hydrodynamic interactions are screened on sufficiently large scales and times. If chains are not entangled, additive local or blob friction gives Rouse model behaviour, $D\propto N^{-1}$ at fixed concentration. For long entangled chains, neighboring chains prevent rapid transverse escape. In the reptation tube picture the chain moves mainly along its contour until it renews the surrounding tube. Contour diffusion scales as $N^{-1}$, the tube-renewal time as $N^3$, and the random-coil size squared as $N$. ThereforeBoth cases ultimately give diffusive centre-of-mass motion, but entangled concentrated chains move much more slowly and retain constraints for longer. The inequality $\varphi \gg {\varphi }^{\ast }$ establishes strong overlap, not by itself entanglement: the latter also requires sufficiently many segments relative to an entanglement length. No numerical entanglement scale or concentrated-solution diffusion coefficient is supplied, so only the conditional regimes and scaling exponents can be fixed here.