Statistical mechanics of dense ionized matter. IV. Density and charge fluctuations in a simple molten salt

Abstract

The results of a molecular-dynamics study of a simple model of a molten salt are reported. The interionic pair potential which is used consists of the Coulombic term an an inverse-power repulsion which is assumed to be the same for all ions. The structure of the liquid is found to be dominated by charge-ordering effects and the calculated equilibrium properties are in good agreement with the predictions of the hypernetted-chain approximation. The relation between the self-diffusion coefficient and the electrical conductivity is discussed, and the observed deviations from the Nernst-Einstein relation in real molten salts are shown to have a natural explanation in terms of short-lived cross correlations. Data on the spectra of charge and particle density fluctuations are presented. At small wave numbers there is a propagating optic-type mode which shows a strong negative dispersion, but no Brillouin peak is seen even at the lowest wave number which is accessible. The data are analyzed in terms of a single-relaxation-time model incorporating the low-order spectral moments, for which we give explicit formulas. The fit achieved is fair, but the low-frequency behavior of the charge fluctuations at small wave numbers is incorrectly reproduced, and there is evidence for the necessity of introducing a second relaxation time. Comparison is made with results previously obtained for the classical one-component plasma.