Elsevier

Chemical Physics

Volume 32, Issue 3, 15 August 1978, Pages 429-435
Chemical Physics

Laser photodissociation of s-tetrazine: Product vibrational excitation

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Abstract

The photosensitive and thermally unstable molecule s-tetrazine decomposes to yield one nitrogen molecule and two HCN molecules. Following pulsed irradiation of tetrazine vapor at 492.3 nm, we have observed time resolved infrared fluorescence from HCN(001). In a similar experiment, small quantities of CO2 were added to the sample cell, and we observed infrared fluorescence from CO2 (001) populated by VV energy transfer. From fluorescence intensity measurements, we have been able to estimate the amount of excitation in certain product vibrations. We conclude that ≈ 1% of the HCN is produced in the (001) state, and the “equivalent” of ≈ 0.1 quantum of N2 vibrational excitation is excited. This latter figure may include some excitation of HCN (ν1), but the measured energy transfer rate coefficients are consistent with N2 excitation. The small amount of HCN(ν3) and N2 vibrational excitation is surprising, as the photodissociation is exothermic by more than 100kcal/mole.

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Research supported in part by the USC Joint Services Electronics Program.

1

On leave from the Soreq Nuclear Research Center, Yavne, Israel.

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