A spectroscopic and computational study of Al(III) complexes in cryolite melts: Effect of cation nature

► We investigate Li, Na and K cryolite melts by Raman spectroscopy and dft. ► A slight red shift of main Raman peaks is observed in the row Li+, Na+, K+. ► A decrease of the half-widths of peaks is observed in the same row. ► Fluoroaluminates and their complexation kinetics play an important role.