ROTATIONAL ANALYSIS OF BANDS OF THE 2900 {\AA} ELECTRONIC TRANSITION OF $SO_{2}$

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1974

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Ohio State University

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Rotational analyses of various bands of the 2900 {\AA} absorption system of $SO_{2}$ have been carried out, from high resolution plates taken with the gas at dry ice temperature. Fairly complete analyses of the three longest wavelength bands observable in the transition (3340 - 3400 {\AA}) show that the upper state structure is r(S - 0) = 1.53 {\AA}, $<$ OS0 = $90^{\circ}$, and that the bands are type C; the transition must be interpreted as the forbidden $\pi\rightarrow\pi^{*}{} ^{1}A_{2} -^{1}A_{1}$ transition, made allowed by Herzberg-Teller interaction through $Q_{3}$ ($b_{2}$). Partial analyses of some of the strong bands near 3000 {\AA} have also been performed. These bands are very similar to the long wavelength bands (chough they are even more severely perturbed), and, in accord with the recent $S^{18}O_{2}$ isotope shift data of Brand and Nanes$^{1}$, must also belong to the $^{1}A_{2} - ^{1}A_{1}$ transition. The intensity of these bands presumably comes from the $n \rightarrow\pi^{*} {}^{1}B_{1} (^{1}\Delta_{g}) - ^{1}A_{1}$ transition; it seems that this transition falls near 3000 {\AA}.

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$^{1}$ J.C.D. Brand and R. Nanes, J. Mol. Spectrosc. 46, 194 (1973).
Author Institution: Department of Chemistry, University of British Columbia

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