[en] Octahedral-type coordination by halogens in the liquid state has been reported for a number of trivalent metal ions from diffraction and Raman scattering experiments on their molten trihalides and from Raman scattering spectroscopy of liquid mixtures of trihalides with alkali halides. We analyze the available data on bond lengths and Raman frequencies by treating an isolated (MX₆)^3- species within a model which adopts charged-soft-sphere interionic potentials supplemented by an account of ionic polarization. The trivalent metal ions that we consider are M = La, Ce, Pr, Nd, Sm, Gd, Dy and Y for X = Cl and M = Al for X = F. The main result of the analysis is the prediction of trends in the soft-sphere repulsive parameters for the trivalent metal ions, leading to estimates of all the vibrational frequencies and the binding energy of such octahedral species. (author). 26 refs, 1 fig., 4 tabs

[en] We discuss the dependence of the stability of tetrahedral complexes in molten halide mixtures on the halogen species. This is done by calculating the equilibrium concentration of (CaBr₄)^2- complexes in calcium-alkali bromide solutions as a function of composition, in comparison with earlier calculations on the calcium-alkali chloride systems. The comparison supports a possible trend of increasing stability from chlorides to bromides, provided that halogen polarizability or chemical bonding contribute appreciably to the binding of a complex. Supporting evidence is noted and further experiments are suggested. (author). 10 refs, 2 figs