HIGH-RESOLUTION STIMULATED RAMAN SPECTROSCOPY OF THE $\nu_{1}$ BAND OF $SiH_{4}$

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1980

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Ohio State University

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A Doppler-limited isotropic Raman spectrum of the symmetric stretching fundamental $(\nu_{1})$ of $^{28}SiH_{4}$ has been recorded using high-sensitivity “quasi-cw” inverse Raman spectroscopy. Unlike the corresponding fundamentals of $^{12}CH_{4}$ (1) and $^{13}CH_{4}$ (2), this band exhibits compact non-overlapping J manifolds that extend over about $5 cm^{-1}$. Since $\nu_{1}$ and the infrared-active stretch $\nu_{3}$ reported by Cabana et al. (3) and the Raman frequencies of $\nu_{1}$ Q (0) through Q(14). The results confirm the infrared analysis (3), in which several perturbation-allowed $\nu_{1}$ transitions were identified in absorption, but the molecular constants are much better determined by the inclusion of the Raman data. Significant intensity perturbations occur at higher J due to a break down of the selection rule $\Delta=0$ (N is the index distinguishing between levels of the same J and rovibrational symmetry), and have been quantitatively accounted for.

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1. A Owyoung, C. W. Patterson, and R. S. McDowell, Chem. Phys. Lett. 59, 156 (1978). 2. R. S. McDowell, C. W. Patterson, and A. Owyoung, J. Chem. Phys., in press. 3. A. Cabana, D. L. Gray, A. G. Robiette, and G. Pierre, Mo1. Phys. 36, 1503 (1978)
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