INFRARED ABSORPTION OF TRANS-CIS $N_{2}O_{3}$ IN ARGON MATRIX
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Date
1997
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Ohio State University
Abstract
Matrix isolation combined with Fourier transform infrared spectroscopy has been employed to investigate the interconversion of $N_{2}O_{3}$ conformers in an argon matrix under pulsed UV laser irradiation. Irradiation of an argon matrix containing NO and $NO_{2}$ with a 355 nm pulsed laser causes the conversion of asym-$N_{2}O_{3}$ to a new conformer, trans-cis $N_{2}O_{3}$. The vibrational assignment of trans-cis $N_{2}O_{3}$ have been performed for the first time. The observed vibrational frequencies are in good agreement with Density Functional Theory (DFT) calculations at BLYP/6-31$G^{*}$ level and {ab initio} calculations at the MP2 level with 6-31$G^{*}$ and 6-311$G^{*}$ basis sets. Upon annealing the Ar matrix, the thermally induced conversion of trans-cis into sym-$N_{2}O_{3}$ takes place predominantly. Irradiation of asym-$N_{2}O_{3}$ with a 266 nm pulsed laser not only leads to the conversion to trans-cis $N_{2}O_{3}$, but sym-$N_{2}O_{3}$ as well. A mechanism of photo-induced isomerization of the $N_{2}O_{3}$ conformers is proposed.
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Author Institution: Laser Chemistry Institute, Fudan University