TEMPERATURE DEPENDENCE OF THE COLLISIONAL ELECTRONIC QUENCHING RATE IN GLYOXAL VAFOR
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Date
1978
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Ohio State University
Abstract
An empirical correlation has been found relating the rate of collision-induced state changes $k_{Q}$ to the depth of the intermolecular potential between the two colliding species $\epsilon_{A^{*} -M}$. Theoretical justification of this finding predicts an inverse dependence of the rate constant on temperature, in $k_{Q}\sim \epsilon_{A}{^{*}}{_{-M}}/kT$. Results obtained for a series of ``inert"" collision partners M destroying the vibrationless level of the $S_{1}$ glyoxal state $A^{*}$ are reported in the temperature range $T = 200-400^{\circ} $K. Increasing $k_{Q}’s$ are observed as the temperature is lowered. Semilog plots of $k_{Q}$ vs $\epsilon_{M}$ provide insight into the excited state well depth $\epsilon_{A}{^{*}}$.
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Author Institution: Department of Chemistry, Indiana University