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The shape of the nonlocal dielectric function of polar liquids and the implications for thermodynamic properties of electrolytes: A comparative study

J. Chem. Phys. 104, 1524 (1996); doi:10.1063/1.470741

Issue Date: 22 January 1996

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Alexei A. Kornyshev
Institut für Energieverfahrenstechnik, Forschungszentrum Jülich GmbH, D-52425 Jülich, Germany,
The A. N. Frumkin Institute of Electrochemistry of the Academy of Sciences, 117071 Moscow, Russia

Godehard Sutmann
Institut für Energieverfahrenstechnik, Forschungszentrum Jülich GmbH, D-52425 Jülich, Germany
Consequences of different forms of the nonlocal dielectric function epsilon(k) of a polar solvent in thermodynamics of electrolytes are studied. This is done with the help of an analytical approximation which covers, as particular cases, different types of results obtained by several groups on the basis of molecular theories or computer simulations. It is shown that the forms of epsilon(k) which include a range of negative values may not contradict experimental data for hydration energies (in contrast to which was argued before) when one goes beyond the simple Born model of an ion and accounts for higher frequency mode contributions. A study of the implications for the activity coefficents shows that oscillations of the interaction energy between ions, following from such forms of epsilon(k), lead to a compensation effect which brings the results closer to the prediction of classical electrostatics and to experimental data. ©1996 American Institute of Physics.
History: Received 27 December 1994; accepted 10 October 1995
Permalink: http://link.aip.org/link/?JCPSA6/104/1524/1
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KEYWORDS and PACS

Keywords
PACS
  • 77.22.Ch
    Dielectrics, piezoelectrics, and ferroelectrics and their properties Dielectric properties of solids and liquids Permittivity (dielectric function)
  • 82.60.Lf
    Physical Chemistry Chemical thermodynamics Thermodynamics of solutions
  • YEAR: 1996

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ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (66)
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