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Theory of the dielectric constant of ice
Authors:J.F. Nagle
Affiliation:Department of Physics, Carnegie-Mellon University, Pittsburgh, Pennsylvania 15213, USA
Abstract:The first result of this paper is to show that the Onsager—Slater theory of the dielectric constant is consistent for some reasoable model of ice in the limit of no intrinsic defects. Accordingly, a model is presented, called the unit model, which has unit cells with no dipole moments for which the Onsager—Slater theory is exact. The second result of this paper is to show that the unit model is physically and chemically realistic. Bjerrum defects are introduced into the model and the relation between the dielectric constant and the Bjerrum defect charge found by Onsager and Dupuis for a less realistic model continues to hold and is satisfied by the experimental values. In a simple point charge approximation the charge distribution determined by the model requirements and the experimentally determined Bjerrum fault charge are found and seem reasonble. Higher order multipole interaction energies are consistent with eviations from pure 1/T dependence of the dielectric constant of real ice with intrinsic defects, can be derived in the context of the unit model. This formula interpolates between the Onsager—Slater formula in the limit of no intrinsic defects and the Kirkwood—Frohlich formula in the limit of many intrinsic defects. For the concentration of defects in real ice the interpolation formula is practically the same as the Onsager—Slater formula and differs from the Kirkwood—Frohlich formula by a factor of nearly 32.
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