### 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 language | English (US) |
---|---|

Pages (from-to) | 4133-4144 |

Number of pages | 12 |

Journal | The Journal of Chemical Physics |

Volume | 78 |

Issue number | 6 |

State | Published - 1983 |

Externally published | Yes |

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### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics

### Cite this

*The Journal of Chemical Physics*,

*78*(6), 4133-4144.

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

Research output: Contribution to journal › Article

*The Journal of Chemical Physics*, vol. 78, no. 6, pp. 4133-4144.

}

TY - JOUR

T1 - The interionic potential of mean force in a molecular polar solvent from an extended RISM equation

AU - Hirata, Fumio

AU - Rossky, Peter J.

AU - Pettitt, Bernard

PY - 1983

Y1 - 1983

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=36749104937&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=36749104937&partnerID=8YFLogxK

M3 - Article

VL - 78

SP - 4133

EP - 4144

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 6

ER -