ROTATIONAL INTENSITIES IN FLUORESCENCE FROM SELECTIVELY EXCITED $S_{2}$

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1975

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Ohio State University

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Intensity measurements have been made on flourescent emissioln from the $B^{3}\Sigma_{u}^{-}$- state of $S_{2}$, selectively excited using Hg line radiation. The ratio of the intensity I of a “satellite” branch (e.g., $T_{R_{31}}$) to that of a ``main” branch (e.g., $T_{R}$) yields information on the triplet splitting parameter $\lambda$. In general, the satellites are weak if $\lambda$ is similar for both electronic states involved in the transition, but stronger if $\lambda$ is much different. The ratio $I(T_{R_{31}})/I(R_{3})$ is $\sim$ 1.9 for emission from $v^{\prime} = 4, J^{\prime} = 13$, while the corresponding ratio for the $v^{\prime} = 1, J^{\prime} = 29$ level is $< 0.05$. The conclusion that $\lambda(B,v^{\prime} = 1)$ is quite different from $\lambda(B,v^{\prime} = 4)$ is in accord with results from a previous comparison of satellite intensities for $J^{\prime}$ near 40 in $v^{\prime} = 3$ and 4.

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This work was supported by the National Science Foundation.
Author Institution: Department of Chemistry, University of Wisconsin

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