Raman spectra of solid, molten, and gaseous gallium trichloride

Separation of GaCl3 from AlCl3 by Solid–Liquid Extraction and Stripping Using Anhydrous n-Dodecane and NaCl

“…Besides the formation of the ionic compound [InCl 2 ]­[GaCl 4 ], the mixed dimer InGaCl 6 may be formed in the mixture of InCl 3 and GaCl 3 , which has been reported in the vapor phase of the InCl 3 –GaCl 3 system by Buraya et al We optimized structures of the relevant compounds in this study by DFT calculations (Figure ) and generated their Raman spectra, which are used to discuss the two possible compounds. Pure GaCl 3 is a dimer (Ga 2 Cl 6 ), and its Raman spectrum has been reported by various researchers. , There is a good match between the calculated Raman spectrum of Ga 2 Cl 6 and the corresponding experimental spectrum (Figure S2), although the shifts for the bands at 244 and 329 cm –1 are relatively large. The good match indicates that the DFT method used in this study is suitable for calculating this compound.…”

“…Pure GaCl 3 is a dimer (Ga 2 Cl 6 ), 39 and its Raman spectrum has been reported by various researchers. 40,41 There is a good match between the calculated Raman spectrum of Ga 2 Cl 6 and the corresponding experimental spectrum (Figure S2), although the shifts for the bands at 244 and 329 cm −1 are relatively large. The good match indicates that the DFT method used in this study is suitable for calculating this compound.…”

Dimeric Molecular Structure of Molten Gallium Trichloride and a Hidden Evolution toward a Possible Liquid–Liquid Transition

“…These characteristic trends show a continuous evolution toward dimer dissociation at higher temperatures; an increasing Ga–Ga separation simultaneously with shorter Cl–Cl distances destabilizes the Ga 2 Cl 6 dimer. Taking into account the planar geometry of GaCl 3 , Figure S1 (Supporting Information), there are two possible scenarios of a liquid–liquid transition, presumably close to the critical temperature The puckered Ga 2 Cl 6 entity transforms first into a planar Ga 2 Cl 6 dimer, similar to that in group 11 trihalides, for example, Au 2 Cl 6 , and then dissociating into two planar GaCl 3 monomers, Figure a–c.…”

“…The latter indicates the dimeric nature of GaCl 3 in benzene. More recently, 15 a Raman study of liquid and gaseous gallium trichloride has revealed the presence of both dimeric and monomeric GaCl 3 species in high-temperature/high vapor pressure conditions.…”

Conductivities of Some Molten Chlorides at Elevated Temperatures II. Electrical Conductivity of Molten Chlorides (InCl3, ZrCl4, HfCl4) with Negative Temperature Coefficients

“…Zirconium and hafnium tetrachlorides form melts consisting mainly of MCl 4 monomers and M 2 Cl 8 dimer molecules (M = Zr, Hf) − with very low values of electrical conductivity about 1 × 10 –4 and 5 × 10 –6 S·cm –1 . It has been proposed in previous work that zirconium and hafnium tetrachlorides dissociated in a very insignificant degree to the MCl 2 2+ , MCl 3 + , MCl 6 2– , and MCl 5 – type ions, which provide weak conductivities of these essentially molecular melts.…”