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 |
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ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry
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Thermodynamic functions as correlation-function integrals. / Koga, Kenichiro; Widom, B.
In: The Journal of Chemical Physics, Vol. 138, No. 11, 114504, 21.03.2013.Research output: Contribution to journal › Article
}
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 -