Competition between singlet and triplet channels in the photoinitiated decomposition of HNCO

The spin-forbidden channel, NH(X 3∑−)+CO, has been observed directly in the photodissociation of jet-cooled HNCO following S1←S0 excitation. The NH(X 3∑−) yield spectrum is obtained in the energy regimes near the thresholds to H+NCO and NH(a 1Δ)+CO channels. The spectrum is similar to the NCO yield...

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Bibliographic Details
Published in:The Journal of chemical physics 1997-05, Vol.106 (17), p.7454-7457
Main Authors: Zyrianov, M., Droz-Georget, Th, Reisler, H.
Format: Article
Language:English
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Summary:The spin-forbidden channel, NH(X 3∑−)+CO, has been observed directly in the photodissociation of jet-cooled HNCO following S1←S0 excitation. The NH(X 3∑−) yield spectrum is obtained in the energy regimes near the thresholds to H+NCO and NH(a 1Δ)+CO channels. The spectrum is similar to the NCO yield spectrum when direct dissociation on S1 is not significant. At photolysis energies >43 400 cm−1, state specific differences between the NH(X 3∑−), NH(a 1Δ) and NCO yield spectra are observed, and at energies >44 000 cm−1 all structure in the NH(X 3∑−) yield spectrum is lost, while the NH(a 1Δ) yield spectrum remains structured. The results are interpreted in terms of the different time scales for intersystem crossing and dissociation.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.473705