THE NATURE OF PHOTOCHEMICAL ISOMERIZATION IN $ClO_{2}$

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1979

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Ohio State University

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The photochemical isomerization of the symmetrical 0C10 isomer to produce unsymmetrical C100 will be discussed. Matrix isolation spectroscopic $studies^{1}$ of this isomerization process will be interpreted to indicate the possible presence of excited states in rare gas matrices. Preliminary gas phase studies will be presented. The results of extensive theoretical calculations indicate that the isomerization process corresponds to an initial sequence \begin{equation} OC10 \tilde{X}^{2} B_{1} \stackrel{hv}{\rightarrow}OC10 \tilde{A}^{2} B_{2} \end{equation} where the allowed nature of the transition (1) is the result of a Herzberg-Teller vibrionic coupling between the $A^{2}B_{2}$ and $B^{2}A_{1}$ states of 0C10 through the asymmetric stretch. Isomerization takes place on the $^{2}B_{2}$ potential resulting in the sequence \begin{equation} OC10 \tilde{A}^{2}B_{2} \rightarrow C100 \tilde{A}^{2}A^{\prime\prime} \end{equation} where a low-lying excited state of C100 1s formed. The $^{2}A^{\prime}$ state deactivates to vibrational levels $(v_{3} \geq 4, 0-0$ stretch) of the ground $^{2}A^{\prime}$ state of C100 which decay very slowly and can be monitored with infrared absorption $spectroscopy.^{1}$

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$^{1}$ A. Arkell and J. Schwager, J. Am. Chem. Soc. 89, 5999 (1967).
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