Forced extension of a wormlike chain in the Gibbs and Helmholtz ensembles

A semiflexible polymer can be stretched by either applying a force to it or by fixing the positions of its endpoints. The two approaches generally yield different results and correspond to experiments performed in either the Gibbs or Helmholtz statistical ensembles. Here, we derive the Helmholtz for...

Full description

Saved in:
Bibliographic Details
Published in:The Journal of chemical physics 2024-02, Vol.160 (8)
Main Authors: Andersen, Nigel T., Chen, Jeff Z. Y.
Format: Article
Language:English
Citations: Items that this one cites
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:A semiflexible polymer can be stretched by either applying a force to it or by fixing the positions of its endpoints. The two approaches generally yield different results and correspond to experiments performed in either the Gibbs or Helmholtz statistical ensembles. Here, we derive the Helmholtz force-extension relationship for the commonly used wormlike-chain model in the strongly stretched regime. By analyzing it in comparison with the Gibbs ensemble result, we show that equivalence between the two relationships is achieved only in the long-chain thermodynamic limit.
ISSN:0021-9606
1089-7690
DOI:10.1063/5.0191727