Results
Title

Combined DFT and ionic model computational study of the effect of alkali metal cations on the structure, bonding and properties of molten cryolites, M<sub>3</sub>AlF<sub>6</sub> (M = li, Na, K, Rb, and Cs).

Authors

Özen, Alimet Sema; Akdeniz, Zehra

Abstract

Ionic melts, in the form of ionic liquids and molten salts, are important in many technological aspects such as metal production and energy applications. Cryolite melts constitute an important family especially for the industrial production of Al. The present computational study aims to analyse the effect of different cations on the structure and properties of Al (III) fluorocomplexes in cryolite melts. Cation effects are discussed as the ion pair interactions due to alkali metal cations of cryolite compounds M3AlF6 with M= Li, Na, K, Rb, or Cs for various microclusters using ionic interaction model (IM) and DFT calculations. DFT results for different ion complexes are compared with the energy calculations using a pseudoclassical model for isolated clusters. QTAIM and ELF analyses were performed to understand the nature of interactions in detail. A link between open-shell interactions and decreased ionic conductivity is proposed within the series of K, Rb, and Cs. Environmental effects, such as temperature and presence of other ions, are investigated in detail by DFT analysis.

Subjects

ION pairs; IONIC conductivity; IONIC interactions; COMPLEX ions; FUSED salts; ALKALI metals; RUBIDIUM

Publication

Physics & Chemistry of Liquids, 2025, Vol 63, Issue 1, p31

ISSN

0031-9104

Publication type

Academic Journal

DOI

10.1080/00319104.2024.2349777