Journal
CHEMICAL PHYSICS
Volume 412, Issue -, Pages 22-29Publisher
ELSEVIER SCIENCE BV
DOI: 10.1016/j.chemphys.2012.11.006
Keywords
Cryolite melts; Alkali cation nature; Raman spectroscopy; Quantum chemical modelling; Density functional theory; Fluoraluminates
Funding
- FWF project [I200-N19]
- Austrian Ministry of Science
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Lithium, sodium and potassium cryolite melts are probed by Raman spectroscopy in a wide range of the melt composition. The experimental data demonstrate a slight red shift of main peaks and a decrease of their half-widths in the row Li+, Na+, K+. Quantum chemical modelling of the systems is performed at the density functional theory level. The ionic environment is found to play a crucial role in the energy of fluoroaluminates. Potential energy surfaces describing the formation/dissociation of certain complex species, as well as model Raman spectra are constructed and compared with those obtained recently for sodium containing cryolite melts (R.R. Nazmutdinov, et al., Spectrochim, Acta A 75 (2010) 1244.). The calculations show that the cation nature affects the geometry of the ionic associates as well as the equilibrium and kinetics of the complexation processes. This enables to interpret both original experimental data and those reported in literature. (C) 2012 Elsevier B.V. All rights reserved.
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