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Electrostatic correlations and the polyelectrolyte self energy

Shen, Kevin and Wang, Zhen-Gang (2017) Electrostatic correlations and the polyelectrolyte self energy. Journal of Chemical Physics, 146 (8). Art. No. 084901. ISSN 0021-9606. doi:10.1063/1.4975777.

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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.

Item Type:Article
Related URLs:
URLURL TypeDescription Paper
Shen, Kevin0000-0001-9715-7474
Wang, Zhen-Gang0000-0002-3361-6114
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.
Funding AgencyGrant Number
NSF Graduate Research FellowshipUNSPECIFIED
Issue or Number:8
Record Number:CaltechAUTHORS:20170224-103032443
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Official Citation:Electrostatic correlations and the polyelectrolyte self energy Kevin Shen and Zhen-Gang Wang The Journal of Chemical Physics 2017 146:8
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:74525
Deposited By: George Porter
Deposited On:24 Feb 2017 19:02
Last Modified:11 Nov 2021 05:27

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