Polymer chain stiffness vs. excluded volume: A Monte Carlo study of the crossover towards the worm-like chain model

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Published 15 November 2010 Europhysics Letters Association
, , Citation Hsiao-Ping Hsu et al 2010 EPL 92 28003 DOI 10.1209/0295-5075/92/28003

0295-5075/92/2/28003

Abstract

When the local intrinsic stiffness of a polymer chain varies over a wide range, one can observe both a crossover from rigid-rod–like behavior to (almost) Gaussian random coils and a further crossover towards self-avoiding walks in good solvents. Using the pruned-enriched Rosenbluth method (PERM) to study self-avoiding walks of up to Nb=50000 steps and variable flexibility, the applicability of the Kratky-Porod model is tested. Evidence for non-exponential decay of the bond-orientational correlations ⟨cos θ(s)⟩ for large distances s along the chain contour is presented, irrespective of chain stiffness. For bottle-brush polymers on the other hand, where experimentally stiffness is varied via the length of side-chains, it is shown that these cylindrical brushes (with flexible backbones) are not described by the Kratky-Porod worm-like chain model, since their persistence length is (roughly) proportional to their cross-sectional radius, for all conditions of practical interest.

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10.1209/0295-5075/92/28003