Past exam of the quantum condensed matter course of the University of Cambridge / 2007 / Section A / A3 / e

In a dilute solution, solvent-mediated hydrodynamic interactions couple distant chain segments. The Zimm model describes the resulting cooperative dynamics: an intermediate-time segment mean-square displacement scales as $t^{2/3}$, while whole-chain translation has $D_Z\sim k_{B}T/({\eta }_{s}R)$. Once internal modes relax, each tagged segment follows the chain's ordinary long-time diffusion, with mean-square displacement asymptotic to $6D_{Z}t$.

In a concentrated solution or polymer melt, hydrodynamic coupling is screened. The unentangled Rouse model has an intermediate $t^{1/2}$ segment regime and whole-chain diffusivity proportional to $N^{-1}$. Long chains with polymer entanglement are additionally confined by neighbouring chains: reptation gives a slower intermediate $t^{1/4}$ regime and an asymptotic chain diffusivity scaling approximately as $N^{-2}$. The time windows depend on segment, entanglement and terminal relaxation times, so these powers do not all describe the same time interval.

After sufficiently long times both dilute and concentrated chains undergo ordinary translational diffusion. The main long-time difference is the coefficient and its chain-length dependence, with entanglement strongly reducing mobility when the chains are long enough; concentration alone does not guarantee an entangled regime.