Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published February 28, 2017 | Published + Submitted
Journal Article Open

Electrostatic correlations and the polyelectrolyte self energy


We address the effects of chain connectivity on electrostatic fluctuations in polyelectrolyte solutions using a field-theoretic, renormalizedGaussian fluctuation (RGF) theory. As in simple electrolyte solutions [Z.-G. Wang, Phys. Rev. E 81, 021501 (2010)], the RGF provides a unified theory for electrostatic fluctuations, accounting for both dielectric and charge correlation effects in terms of the self-energy. Unlike simple ions, the polyelectrolyte self energy depends intimately on the chain conformation, and our theory naturally provides a self-consistent determination of the response of intramolecular chain structure to polyelectrolyte and salt concentrations. The effects of the chain-conformation on the self-energy and thermodynamics are especially pronounced for flexible polyelectrolytes at low polymer and salt concentrations, where application of the wrong chain structure can lead to a drastic misestimation of the electrostatic correlations. By capturing the expected scaling behavior of chain size from dilute to semi-dilute regimes, our theory provides improved estimates of the self energy at low polymer concentrations and correctly predicts the eventual N-independence of the critical temperature and concentration of salt-free solutions of flexible polyelectrolytes. We show that the self energy can be interpreted in terms of an infinite-dilution energy μ^(el)_(m,0) and a finite concentration correlation correction μ^(corr) which tends to cancel out the former with increasing concentration.

Additional Information

© 2017 AIP Publishing LLC. (Received 11 November 2016; accepted 26 January 2017; published online 23 February 2017) The authors would like to thank Bilin Zhuang, Rui Wang, Pengfei Zhang, and Marco Heinen, for helpful discussions. Special thanks go to Professor Jian Qin for his insightful comments on our manuscript. K.S. acknowledges support by the NSF-GRFP fellowship.

Attached Files

Published - 1_2E4975777.pdf

Submitted - 1701.00214.pdf


Files (2.9 MB)
Name Size Download all
956.6 kB Preview Download
2.0 MB Preview Download

Additional details

August 19, 2023
October 24, 2023