Far infrared and low frequency gas phase Raman spectra, vibrational assignment, and conformational stability of 1-chloro-2-methylpropane and 1-bromo-2-methylpropane

Abstract

The Raman (3200—10cm −1) and infrared (3200—50 cm −1) spectra of gaseous and solid 1-chloro-2-methylpropane and 1-bromo-methylpropane, as well as the Raman spectra of the liquids, have been recorded and assigned. The gauche asymmetric torsion of the 1-chloro-2-methylpropane molecules has been observed at 110 cm −1 in the Raman spectrum of the gas. For the 1-bromo-2-methylpropane molecule, both the trans and gauche asymmetric torsions have been observed at 106.70 and 103.94 cm −1, respectively, along with three additional transitions for the gauche conformer. From these data, the asymmetric potential function for the bromide molecules to V 1 = —493 ±16, V 2 = 595 ± 18, and V 3 = 2006 ± 6 cm −1 with the trans conformer being more stable than the gauche conformer by 44 ± 20 cm −1. The trans form is found experimentally to be more stable in the liquid phase by 30 ± 14 cm −1 (83 ± 40 cal mol −1). From the relative intensities, in the Raman spectra, of the CCl stretches measured as a function of temperature, the gauche conformer of the chloride molecules to be 167 ± 71 cm −1 (479 ± 203 cal mol −1) more stable than the trans conformer in the gas phase, and 73 ± 10 cm −1 (208 ± 29 cal mol −1) more stable in the liquid phase. The methyl torsions for the gauche and trans conformers of both molecules are tentatively assigned in the gas phase and the barriers have been calculated. The results of this study are compared with previous studies on these molecules.