THE $\nu_{3}$ RAMAN BAND OF METHANE

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1961

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Ohio State University

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The matrix elements of the polarizability tensor for the transitions involved in the triply degenerate vibrational bands of methane-type molecules have been calculated- It is found that the general Raman selection rules $\Delta J=0, \pm 1, \pm 2$ have the following symmetry restrictions: \[ \begin{array}{l} for\;\Delta J=0, \pm 2\;only\;A_{1} \leftrightarrow A_{1}, A_{2} \leftrightarrow A_{2}, E \leftrightarrow E, F_{1} \leftrightarrow F_{1}, F_{2} \leftrightarrow F_{2}\\ for\;\Delta J= \pm 1,\;only\;A_{1} \leftrightarrow A_{2}, E \leftrightarrow E, F_{1} \leftrightarrow F_{2}, \end{array} \] The intensity patterns for the fine structures of the rotational lines have been computed: corresponding lines in all 15 branches can be classified into four groups within which the intensity patterns differ only in magnitude. The calculated spectrum is in agreement with the structure observed in the $\nu_{3}$ Raman band of $CH_{4}$ photographed at high resolution and has- made possible the analysis of this complex band.

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Author Institution: Division of Pure Physics, National Research Council

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