Abstract
Spurred by an experimental controversy in the literature, we investigate the end-monomer dynamics of semiflexible polymers through Brownian hydrodynamic simulations and dynamic mean-field theory. Precise experimental observations over the past few years of end-monomer dynamics in the diffusion of double-stranded DNA have given conflicting results: one study indicated an unexpected Rouse-like scaling of the mean-squared displacement (MSD) 〈 2(t))〉 ∼ t 1/2 at intermediate times, corresponding to fluctuations at length scales larger than the persistence length but smaller than the coil size; another study claimed the more conventional Zimm scaling 〈r 2(t)〉 ∼ t 2/3 in the same time range. Using hydrodynamic simulations as well as analytical and scaling theories, we find a novel intermediate dynamical regime where the effective local exponent of the end-monomer MSD, α(t) = d(log〈r 2(t)〉)/d(log t) drops below the Zimm value of 2/3 for sufficiently long chains. The deviation from the Zimm prediction increases with chain length, though it does not reach the Rouse limit of 1/2. The qualitative features of this intermediate regime, found in simulations and in an improved mean-field theory for semiflexible polymers, in particular the variation of α(t) with chain and persistence lengths, can be reproduced through a heuristic scaling argument. Anomalously low values of the effective exponent a are explained by hydrodynamic effects related to the slow crossover from dynamics on length scales smaller than the persistence length to dynamics on larger length scales.
Original language | English |
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Pages (from-to) | 860-875 |
Number of pages | 16 |
Journal | Macromolecules |
Volume | 42 |
Issue number | 3 |
DOIs | |
State | Published - 10 Feb 2009 |
ASJC Scopus subject areas
- Organic Chemistry
- Polymers and Plastics
- Inorganic Chemistry
- Materials Chemistry