ROTATIONAL RELAXATION WITHIN $S_{2} (B^{3}\Sigma^{-}_{u}, v''=4)$

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1979

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Ohio State University

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Rates for collision-induced transfer from a single rotational level ($N^{\prime\prime}=40, J^{\prime\prime}=41$) to other individual rotational levels within the $v^{\prime\prime}=4$ vibrational level of the $B^{3}\Sigma^{-}_{u}$ state of $S_{2}$ are reported. The $S_{2}$ was excited by atomic Zn line radiation, and rotationally resolved fluorescence measurements were used to determine the rates for the collision partners He, Ar and Xe. Single collision multiquantum transfer is found, but (for $F_{1} \rightarrow F_{1}$ transfer) with a magnitude which decreases with $|\Delta N|$. For small $\Delta N, F_{1} \rightarrow F_{1}$ transfer is preferred over $F_{1} \rightarrow F_{3}, F_{2}$. A surprisal plot for $F_{1} \rightarrow F_{1}$ transfer is linear for $|\Delta N|\geq 4$ with the following slopes: He, 4.6; Ar, 3.4; Xe: 1.9. These results and those for vibrational and total rotational $relaxation^{1}$ indicate a brief collision encounter.

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$^{1}$T. A. Caughey and D. R. Crosley, J. Chem. Phys. 69, 3379 (1978).
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