Ionic excesses and entropies in mean-field screening models

We examine how the mean-field ionic screening excess associated with a charged macromolecule depends upon the macromolecule's geometric conformation and net charge. Our approach involves expanding about Debye-Hückel theory, which allows us to derive a series of general results that establish ex...

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Bibliographic Details
Published inSoft matter Vol. 8; no. 36; pp. 9368 - 9375
Main Authors Landy, Jonathan, McIntosh, D. B, Saleh, O. A, Pincus, P
Format Journal Article
LanguageEnglish
Published 01.01.2012
Subjects
Charge
Charging
Entropy
Free energy
Joints
Macromolecules
Polyelectrolytes
Screening
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Summary:We examine how the mean-field ionic screening excess associated with a charged macromolecule depends upon the macromolecule's geometric conformation and net charge. Our approach involves expanding about Debye-Hückel theory, which allows us to derive a series of general results that establish explicit connections between the ionic excess, non-linear screening mechanisms, and the mobile ion entropy. We conclude with an analysis of the ionic screening entropy in familiar models for polyelectrolyte force-extension behavior, and we find the changes in this entropy are often quite substantial relative to the total free energy differences characterizing a polyelectrolyte's extended and compact states. We examine how the mean-field ionic screening excess associated with a charged macromolecule depends upon the macromolecule's geometric conformation and net charge.
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ISSN:1744-683X
1744-6848
DOI:10.1039/c2sm25608h