Past exam of the MPhil in micro- and nanotechnology enterprise course of the University of Cambridge / 2021 / Paper 2 / Section B / 22 / iii

In the imposed free-draining polymer friction model, the drag coefficients of the $N$ monomers add, giving ${\zeta }_1=N(6\pi \eta a)$ and $D_1=k_{B}T/(6\pi \eta aN)$. Taking the same three-dimensional centre-of-mass RMS convention as part (ii),The polymer is a one-dimensional connected contour, but that alone does not restrict its centre of mass to one spatial axis. If the intended coordinate is instead literal one-dimensional curvilinear motion along an entanglement tube, its RMS contour displacement is $\sqrt{2D_{1}t}=\sqrt{k_{B}Tt/(3\pi \eta aN)}$. That is a different coordinate and should not be compared with a three-dimensional displacement without stating the conversion/model.

Additive local drag is the free-draining Rouse model approximation. It neglects long-range solvent-mediated hydrodynamic interactions and is not a complete theory of an entangled chain. In a tube/reptation description, curvilinear diffusion can scale as $N^{-1}$ while long-time spatial centre-of-mass diffusion scales as $N^{-2}$ after the chain renews its tube. Conversely a dilute unentangled coil can exhibit Zimm model hydrodynamic coupling. Monomer motion, centre-of-mass motion and contour sliding therefore cannot all be identified with the same displacement law.