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CORIOLIS EFFECTS AND INTENSITY BORROWING IN THE OUT-OF-PLANE BENDING FUNDAMENTALS OF HCOCl AND DCOCl.

Please use this identifier to cite or link to this item: http://hdl.handle.net/1811/29893

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Title: CORIOLIS EFFECTS AND INTENSITY BORROWING IN THE OUT-OF-PLANE BENDING FUNDAMENTALS OF HCOCl AND DCOCl.
Creators: Joo, D.- L.; Clouthier, Dennis J.; Merer, A. J.
Issue Date: 1995
Abstract: The $\nu_{6}$ (out-of-plane bending) fundamentals of the transient molecules formyl chloride, HCOCl, and deuteroformyl chloride, DCOCl, have been recorded at high resolution and rotationally analyzed. In HCOCl, the strong lines obey C-type selection rules although there are many weaker lines involving $\Delta K_{a} = 0$. Although ab initio calculations suggest that the $\nu_{6}$ fundamental should be too weak to be observed, it gains intensity by Coriolis interaction with the $\nu_{4}$ fundamental $193 cm^{-1}$ to lower energy, accounting for the presence of the $\Delta K_{a} = 0$ lines. Perturbations due to the $2 \nu_{5}$ level at higher energy have also been observed and fitted with a two-state interaction model. In DCOCl, the $\nu_{6}$ band has the appearance of an A-type band, as the $\Delta K_{a} = 0$ lines predominate and the C-type component could not be found. In this case, the intensity borrowing from the $\nu_{4}$ fundamental $81 cm^{-1}$ lower in energy predominates, overwhelming the very weak $\nu_{6}$ band. A weak $\Delta K_{a} = |2|$ perturbation was found at high ${K^{\prime}}_{a}$ values allowing us to fit the $\nu_{6}$ and $\nu_{4}$ bands simultaneously with a single interaction constant.
URI: http://hdl.handle.net/1811/29893
Other Identifiers: 1995-FA'-03
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