Raman Line Shapes in Liquid \(CH_3I\) and \(CD_3I\)
Citation
Goldberg, H. S. and Peter S. Pershan. 1973. Raman line shapes in liquid \(CH_3I\) and \(CD_3I\). Journal of Chemical Physics 58(9): 3816-3827.Abstract
The six fundamental bands of \(CH_3I\) and \(CD_3I\), both as pure liquids and in solution with \(CS_2\), have been studied in order to obtain information about the molecular rotational and vibrational dynamics. Emphasis was placed on the features of the spectra that can be interpreted independent of a particular model. An examination for Boltzmann asymmetry in the \(A_1\) and E bands indicates that the former, being symmetric, are amenable to classical description, while the latter, being asymmetric, definitely require quantum mechanical interpretations. With respect to the validity of the assumption that rotation‐vibration coupling can be ignored, we give evidence of substantial coupling effects in a nondegenerate \(A_1\) mode \((\nu1)\) as well as in the doubly degenerate E modes. We emphasize that, in attempting to obtain dynamical information, several bands of any given liquid must be studied and compared in order to decide which can be used with confidence in a detailed analysis. The consistency of the rotational diffusion model for describing the tumbling motion of the methyl iodide molecules has been confirmed.Terms of Use
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