The interionic potential of mean force in a molecular polar solvent from an extended RISM equation

Fumio Hirata, Peter J. Rossky, Bernard Pettitt

Research output: Contribution to journalArticle

246 Citations (Scopus)

Abstract

The generalization of a recently proposed extension of the RISM integral equation to infinitely dilute isolated ions and ion pairs in polar, interaction site model, molecular solvents is outlined. An essential element of the development is the explicit separation of the contributions which yield a continuum dielectric solvent model from the remainder. Thus, it is only for this correction that one relies on the integral equation. Application is made to a system consisting of a diatomic polar solvent and atomic ions of varied charge and radius. The results of these calculations show that the present approach produces sensible qualitative features of ionic solvation including an appropriately varying degree of solvent orientational saturation with ionic charge and radius. Correspondingly, the calculated interionic potentials of mean force reproduce the same basic features manifest in already available studies of dipolar hard sphere solvents, including the positions of oscillatory features in the structure and the relatively short spatial range of the corrections to the continuum dielectric theory. A quantitative evaluation of the accuracy of the present predictions is not possible with presently available data.

Original languageEnglish (US)
Pages (from-to)4133-4144
Number of pages12
JournalThe Journal of Chemical Physics
Volume78
Issue number6
StatePublished - 1983
Externally publishedYes

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Ions
Integral equations
integral equations
continuums
ions
radii
Solvation
solvation
saturation
evaluation
predictions
interactions

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

The interionic potential of mean force in a molecular polar solvent from an extended RISM equation. / Hirata, Fumio; Rossky, Peter J.; Pettitt, Bernard.

In: The Journal of Chemical Physics, Vol. 78, No. 6, 1983, p. 4133-4144.

Research output: Contribution to journalArticle

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