Combination of the matrix isolation and the isotropic substitution techniques: Vibrational spectra and molecular constants of titanium tetrachloride and germanium tetrachloride

Abstract

The i.r. spectra of titanium tetrachloride and germanium tetrachloride in argon matrices have been recorded in the region of the ν 3(F 2) fundamental. The same has been done for the samples 48TiCl 4, Ti 35Cl 4, 74GeCl 4 and Ge 35Cl 4. In this manner assignments could be made with a high order of certainty. The same region has been studied for the pure isotopic species 48Ti 35Cl 4 and 48Ti 35Cl 4, in the gas phase. Similarly, the spectra of the isotopically pure species of germanium tetrachloride, 74Ge 35Cl 4 and 74Ge 37Cl 4, and of the normal compound have been recorded in the gas phase for both the F 2 modes for which Coriolis coupling constants were calculated from the i.r. band contours. Using six independent isotopic shifts for titanium tetrachloride, four ζ-values and three isotopic shifts for germanium tetrachloride as additional data, force constants have been calculated. The force field for both molecules have much smaller error limits when compared with those previously reported.