Calculation of Raman intensities for the torsional vibrations of ethyl halides
Raman intensities are calculated for the torsional vibrations of CH3CH2Cl, CH3CH2Br, CH3CH2I, CH3CHCl2, and CH3CHBr2 using an anisotropic atom‐point dipole interaction model to calculate the elements of the molecular polarizability tensor. The calculated relative intensities for the members of the Δv = 2 torsional overtone progression of each of the ethyl halides are in good agreement with experiment. It is predicted that electrically anharmonic terms contribute substantially to the Raman intensities of these transitions. The Δv = 1 torsional transitions of the five molecules are predicted to be 20–30 times more intense than the overtones (although these transitions are not observed because of broadband contours and interference from other vibrational modes). Electrically anharmonic terms in the polarizability expansions also contribute substantially to the intensity of the fundamentals.
This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Bocian, David F. et al., The Journal of Chemical Physics 76, no. 10 (1982): 4828-4833. and may be found at https://doi.org/10.1063/1.442801.
Bocian, David F., G. Alan Schick, J. Kathleen Hurd, and Robert R. Birge. "Calculation of Raman intensities for the torsional vibrations of ethyl halides." The Journal of Chemical Physics 76, no. 10 (1982): 4828-4833.
The Journal of Chemical Physics