DETERMINATION OF THE $\nu_{9}$ BAND CENTER THROUGH THE FIRST HIGH-RESOLUTION ANALYSES OF THE $\nu_{8}$ and $\nu_{8} + \nu_{9}$ SPECTRAL REGIONS OF $^{35}C1ONO_{2}$

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2003

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Ohio State University

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A ro-vibrational analysis of the C-type $\nu_{8}$ fundamental band of $^{35}C1ONO_{2}$ as well as the hot band, $\nu_{8} + \nu_{9} - \nu_{9}$, has been carried out using a Fourier-transform infrared spectrum of natural chlorine nitrate. This spectrum was recorded with a resolution of $0.00094 cm^{-1}$ at a temperature of 190 K. Accurate upper state constants have been determined for both bands including the following band centers: $\nu_{0}(\nu_{8}) = 711.20763(9)$ and $\nu_{0}(\nu_{8} + \nu_{9} - \nu_{9}) = 714.9050(12) cm^{-1}$. These constants have been used, together with a transition moment operator which takes into account the observed Herman-Wallis effect, to successfully model the experimental spectrum. Moreover the constants of the $8^{1}9^{1}$ state have been used to model the $\nu_{8}+\nu_{9}$ band, allowing us to assign nearly 100 Q-branch transitions and, therefore, to determine the band center of the $\nu_{8} + \nu_{9}$ band, $\nu_{0}(\nu_{8} +\nu_{9}) = 838.6269(15) cm^{-1}$. Consequently we are able for the first time to obtain a precise band center of $\nu_{9} : \nu_{0}(\nu_{9}) = 123.7219(20) cm^{-1}$. Finally this establishes unambiguously that the band at $714.9 cm^{-1}$ previously attributed to $\nu_{5} + \nu_{7} - \nu_{9}$ is actually the $\nu_{8} + \nu_{9} - \nu_{9}$ hot band.

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Author Institution: Laboratoire de Photophysique Mol\'{e}culaire, C.N.R.S., B\^{a}t. 350, Universit\'{e} Paris-Sud; Optical Technology Division, NIST; Optical Technology Division, Institute for Opto-electronics

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