Evidence for many-body interactions in the structure of molten alkali chlorides

An inversion of the measured partial structure factors of molten sodium chloride is attempted in order to assess some qualitative features of interionic forces in the melt. We start from a calculation of liquid structure and thermodynamic properties by means of a refined theory based on interionic pair potentials determined from properties of the solid phase. This yields very good agreement with the measured values of the internal energy and the compressibility of the liquid, whereas discrepancies with the observed structure are mainly localized in the region of interionic distances outside the minimum of the cation-anion potential. These discrepancies, when interpreted in terms of effective pair potentials in the melt through inversion of the structural data, strongly suggest the presence of many-body effects, insofar as such effective pair potentials oscillate with the local liquid structure and are inconsistent with the measured thermodynamic quantities. A similar analysis of data on molten rubidium and cesium chloride, though harder to carry out quantitatively, supports the above conclusion.