Vibrational modes and structures of lanthanide halide–alkali halide binary melts LnBr3–KBr (Ln=La, Nd, Gd) and NdCl3–ACl (A=Li, Na, K, Cs)

Abstract

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Internal cation mobility in molten CsCl–NdCl3 system at 1073K

“…3). It is consistent with the results of Raman spectroscopy investigations of these systems [14], providing evidences for increasing stability of [NdCl 6 ] 3− complexes with the increase of alkali metal atomic number in solutions with molar fraction of NdCl 3 ≤ 0.25. In more concentrated solutions, changes of internal mobility of Nd 3+ are small, and this fact, according to some authors [5,6], suggests that electric charge in these melts is transferred primarily by Ln 3+ cations and chloride anions.…”

“…(5) and seem to suggest the increase of neodymium cations mobility at low concentrations of NdCl 3 . However, if the decrease of Nd 3+ mobility at medium concentrations of neodymium chloride is validated by formation of complexes in the melt [14], there are no arguments for the increase of the mobility at low concentrations. This range of concentrations should be investigated more carefully, especially for alkali metals with higher atomic number (cesium in the first place, but also rubidium and potassium), also due to negative values of Nd 3+ ions mobility in the CsCl-NdCl 3 system at y Nd < ≈0.6, suggesting 'hauling' effect of chloride ions on neodymium cations due to stronger interactions in negatively charged complex forms.…”

Phase diagram of NdI3–RbI pseudo-binary system. Thermodynamic properties of solid compounds

“…The model used for describing the properties of liquid phase in the investigated system has significant influence on the result of the CALPHAD calculation. The liquid phase of lanthanide(III) halide- alkali metal halide systems is an associated liquid [19]. Existence of the associates in a system always results in a deviation from the behavior of regular solutions.…”

Phase diagram and electrical conductivity of the CeBr3–RbBr binary system

“…Raman spectroscopic investigations [29] showed that octahedral LnBr 6 3− ions are formed in LnBr 3 -MBr liquid mixtures. These ions constitute the predominant species in the MBr-rich liquid mixtures.…”