### Abstract

Calculations on the electrostatic free energy of solvation of Rb^{+} (and also Br^{-}) in acetonitrile have been carried out by using various functions that relate the local solvent dielectric constant to distance from the centre of an ion immersed in the solvent. A simple one-step dielectric constant-distance function yields a calculated value in good agreement with the experimentally observed value; this agreement does not depend on any arbitrary single-ion convention. The new dielectric constant profile suggested by Stiles leads generally to too negative a calculated value, as does the Born equation, but an amended profile of similar mathematical form to the function used by Stiles also leads to good agreement between calculated and observed values. It is suggested that although mathematical functions of dielectric constant-distance may be selected on the basis of agreement between calculation and experiment and of convenience of use, not too much physical significance should necessarily be attributed to these functions.

Original language | English |
---|---|

Pages (from-to) | 1273-1279 |

Number of pages | 7 |

Journal | Australian Journal of Chemistry |

Volume | 35 |

Issue number | 7 |

DOIs | |

Publication status | Published - 1982 |

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### ASJC Scopus subject areas

- Chemistry(all)

### Cite this

*Australian Journal of Chemistry*,

*35*(7), 1273-1279. https://doi.org/10.1071/CH9821273

**Calculations on Ionic Solvation. VII* The Free Energy of Solvation of Ions Calculated from Various Local Solvent Dielectric Constant-Distance Functions.** / Abraham, Michael H.; Liszi, J.; Kristof, Erzsébet.

Research output: Contribution to journal › Article

*Australian Journal of Chemistry*, vol. 35, no. 7, pp. 1273-1279. https://doi.org/10.1071/CH9821273

}

TY - JOUR

T1 - Calculations on Ionic Solvation. VII* The Free Energy of Solvation of Ions Calculated from Various Local Solvent Dielectric Constant-Distance Functions

AU - Abraham, Michael H.

AU - Liszi, J.

AU - Kristof, Erzsébet

PY - 1982

Y1 - 1982

N2 - Calculations on the electrostatic free energy of solvation of Rb+ (and also Br-) in acetonitrile have been carried out by using various functions that relate the local solvent dielectric constant to distance from the centre of an ion immersed in the solvent. A simple one-step dielectric constant-distance function yields a calculated value in good agreement with the experimentally observed value; this agreement does not depend on any arbitrary single-ion convention. The new dielectric constant profile suggested by Stiles leads generally to too negative a calculated value, as does the Born equation, but an amended profile of similar mathematical form to the function used by Stiles also leads to good agreement between calculated and observed values. It is suggested that although mathematical functions of dielectric constant-distance may be selected on the basis of agreement between calculation and experiment and of convenience of use, not too much physical significance should necessarily be attributed to these functions.

AB - Calculations on the electrostatic free energy of solvation of Rb+ (and also Br-) in acetonitrile have been carried out by using various functions that relate the local solvent dielectric constant to distance from the centre of an ion immersed in the solvent. A simple one-step dielectric constant-distance function yields a calculated value in good agreement with the experimentally observed value; this agreement does not depend on any arbitrary single-ion convention. The new dielectric constant profile suggested by Stiles leads generally to too negative a calculated value, as does the Born equation, but an amended profile of similar mathematical form to the function used by Stiles also leads to good agreement between calculated and observed values. It is suggested that although mathematical functions of dielectric constant-distance may be selected on the basis of agreement between calculation and experiment and of convenience of use, not too much physical significance should necessarily be attributed to these functions.

UR - http://www.scopus.com/inward/record.url?scp=84970567106&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84970567106&partnerID=8YFLogxK

U2 - 10.1071/CH9821273

DO - 10.1071/CH9821273

M3 - Article

AN - SCOPUS:84970567106

VL - 35

SP - 1273

EP - 1279

JO - Australian Journal of Chemistry

JF - Australian Journal of Chemistry

SN - 0004-9425

IS - 7

ER -