Photodissociation dynamics of C{sub 3}H{sub 5}I in the near-ultraviolet region
- Department of Chemistry, Graduate School of Science, Hiroshima University, Kagamiyama 1-3-1, Higashi-Hiroshima, Hiroshima 739-8526 (Japan)
The ultraviolet photodissociation dynamics of allyl iodide (C{sub 3}H{sub 5}I) have been studied by ion-imaging at 266 nm and 213 nm. These photolysis wavelengths are located in the two lowest absorption bands in the near-ultraviolet region. The atomic iodine products were detected by [2+1] resonantly enhanced multiphoton ionization spectroscopy. The spectra showed that the branching fraction for the spin-orbit excited ({sup 2}P{sub 1/2}) state was larger than that for the ground ({sup 2}P{sub 3/2}) state at both photolysis wavelengths. The state-resolved scattering images of iodine showed two maxima in the velocity distributions in the {sup 2}P{sub 3/2} state and a single peak in the {sup 2}P{sub 1/2} state. The spin-orbit specificity indicates that the C−I bond cleavage at both absorption bands is governed by the dissociative n{sub I}σ{sup *}{sub C−I} potential energy surfaces. The nascent internal energy distribution of the allyl radical (C{sub 3}H{sub 5}) counter product, which was obtained by the analysis of the state-resolved scattering distributions, showed a marked difference between the photolysis at 266 nm and 213 nm. The generation of the colder C{sub 3}H{sub 5} with the higher translational energy at 266 nm implied the direct photoexcitation to the n{sub I}σ{sup *}{sub C−I} repulsive surfaces, whereas the internally hot C{sub 3}H{sub 5} at 213 nm was ascribed to the local π{sub CC}π{sup *}{sub CC} photoinitiation in the allyl framework followed by predissociation to the n{sub I}σ{sup *}{sub C−I} states.
- OSTI ID:
- 22308377
- Journal Information:
- Journal of Chemical Physics, Vol. 141, Issue 10; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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