On the reduction of many‐body dielectric theories to the Onsager equation
- 1 August 1974
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 61 (3) , 889-893
- https://doi.org/10.1063/1.1682030
Abstract
An approximate theory for the dielectric constant ε of a dense polar fluid was derived by Ramshaw, Schaefer, Waugh, and Deutch (RSWD). In the present article, the RSWD theory is generalized and made rigorous by another method of derivation. The result is a rigorous expression for ε which differs from the RSWD expression by the presence of a fluctuation term. Both the rigorous expression and the RSWD expression are then specialized to the Onsager model. It is found that the rigorous expression for ε reduces to the Onsager equation, but that the RSWD expression does not because the fluctuation term is nonzero (and nonnegligible) for the Onsager model. The well‐known discrepancy between the Onsager equation and the theory of Harris and Alder is found to have the same origin.Keywords
This publication has 17 references indexed in Scilit:
- On the Molecular Theory of Dielectric Polarization in Rigid-Dipole FluidsThe Journal of Chemical Physics, 1971
- Dielectric Polarization and Alignment and the Structure of Polar FluidsThe Journal of Chemical Physics, 1971
- Statistical Theory of the Dielectric Constant of an Imperfect GasPhysics of Fluids, 1961
- On the molecular theory of dielectric polarizationPhysica, 1958
- A theory of the dielectric polarization of polar substancesProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1956
- Contributions of Fluctuations and Anisotropy to Dielectric Polarization in Polar SubstancesThe Journal of Chemical Physics, 1955
- The dielectric constant of an imperfect non-polar gasTransactions of the Faraday Society, 1955
- Dielectric Polarization in Polar SubstancesThe Journal of Chemical Physics, 1953
- The Dielectric Polarization of Polar LiquidsThe Journal of Chemical Physics, 1939
- Electric Moments of Molecules in LiquidsJournal of the American Chemical Society, 1936