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Charge oscillations in Debye-Hückel theory

1997/05/22 by Benjamin P. Lee, Michael E. Fisher · 2 citations
Chemical Engineering · Chemistry · Physics and Astronomy · #Chemical Thermodynamics and Molecular Structure #Chemical and Physical Properties in Aqueous Solutions #Thermodynamic properties of mixtures #cond-mat.soft #cond-mat.stat-mech

paper · pdf · doi:10.1209/epl/i1997-00402-x

published as Europhys. Lett. 39, 611 (1997) · 6 pages, EuroPhys.sty (now available on archive), 1 eps figure

arxiv created 1997/05/22 · openalex publication_date 1997/09/15 · arxiv updated 2009/11/30 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/30

Abstract

The recent generalized Debye-Hückel (GDH) theory is applied to the calculation of the charge-charge correlation function, G ZZ ( r ). The resulting expression satisfies both i) the charge neutrality condition and ii) the Stillinger-Lovett second-moment condition for all T and ρ N , the overall ion density, and iii) exhibits charge oscillations for densities above a "Kirkwood line" in the (ρ N , T )-plane. This corrects the normally assumed DH charge correlations, and, when combined with the GDH analysis of the density correlations, leaves the GDH theory as the only complete description of ionic correlation functions, as judged by i)–iii), iv) exact low-density (ρ N , T ) variation, and v) reasonable behavior near criticality.

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