### Abstract

Expressions of some thermodynamic functions as correlation-function integrals, such as the Ornstein-Zernike integral, the Kirkwood-Buff integrals, and the integral formulas for virial coefficients, are recalled. It is noted, as has been remarked before, that the choice of molecular centers from which intermolecular distances are measured is arbitrary and that different choices lead to different forms of the correlation functions but that the integrals must be independent of those choices. This is illustrated with the second virial coefficients of hard spheres in one, two, and three dimensions, with that of gaseous propane in three dimensions, and with computer simulations of the pair correlations in water and in a dilute aqueous solution of propane.

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

Article number | 114504 |

Journal | The Journal of Chemical Physics |

Volume | 138 |

Issue number | 11 |

DOIs | |

Publication status | Published - Mar 21 2013 |

### Fingerprint

### ASJC Scopus subject areas

- Physics and Astronomy(all)
- Physical and Theoretical Chemistry

### Cite this

*The Journal of Chemical Physics*,

*138*(11), [114504]. https://doi.org/10.1063/1.4795498

**Thermodynamic functions as correlation-function integrals.** / Koga, Kenichiro; Widom, B.

Research output: Contribution to journal › Article

*The Journal of Chemical Physics*, vol. 138, no. 11, 114504. https://doi.org/10.1063/1.4795498

}

TY - JOUR

T1 - Thermodynamic functions as correlation-function integrals

AU - Koga, Kenichiro

AU - Widom, B.

PY - 2013/3/21

Y1 - 2013/3/21

N2 - Expressions of some thermodynamic functions as correlation-function integrals, such as the Ornstein-Zernike integral, the Kirkwood-Buff integrals, and the integral formulas for virial coefficients, are recalled. It is noted, as has been remarked before, that the choice of molecular centers from which intermolecular distances are measured is arbitrary and that different choices lead to different forms of the correlation functions but that the integrals must be independent of those choices. This is illustrated with the second virial coefficients of hard spheres in one, two, and three dimensions, with that of gaseous propane in three dimensions, and with computer simulations of the pair correlations in water and in a dilute aqueous solution of propane.

AB - Expressions of some thermodynamic functions as correlation-function integrals, such as the Ornstein-Zernike integral, the Kirkwood-Buff integrals, and the integral formulas for virial coefficients, are recalled. It is noted, as has been remarked before, that the choice of molecular centers from which intermolecular distances are measured is arbitrary and that different choices lead to different forms of the correlation functions but that the integrals must be independent of those choices. This is illustrated with the second virial coefficients of hard spheres in one, two, and three dimensions, with that of gaseous propane in three dimensions, and with computer simulations of the pair correlations in water and in a dilute aqueous solution of propane.

UR - http://www.scopus.com/inward/record.url?scp=84875714672&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84875714672&partnerID=8YFLogxK

U2 - 10.1063/1.4795498

DO - 10.1063/1.4795498

M3 - Article

C2 - 23534646

AN - SCOPUS:84875714672

VL - 138

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 11

M1 - 114504

ER -