Charged Particle Imaging of the Deprotonated Octatrienoic Acid Anion: Evidence for a Photoinduced Cyclization Reaction
| Autor: | Jan R. R. Verlet, James N. Bull, Christopher W. West |
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| Rok vydání: | 2016 |
| Předmět: |
010304 chemical physics
Electronic structure 010402 general chemistry Polyene Photochemistry 01 natural sciences Dissociation (chemistry) Charged particle 0104 chemical sciences Ion chemistry.chemical_compound Deprotonation chemistry X-ray photoelectron spectroscopy 0103 physical sciences General Materials Science Physical and Theoretical Chemistry Isomerization |
| Zdroj: | The journal of physical chemistry letters, 2016, Vol.7(22), pp.4635-4640 [Peer Reviewed Journal] |
| ISSN: | 1948-7185 |
| Popis: | Photoelectron spectroscopy of the deprotonated octatrienoic acid anion, [C7H9–CO2]−, shows the formation of [C7H9]− and loss of H– at hν = 4.13 eV. Using velocity map imaging, the H– fragment was characterized to have a Boltzmann-like kinetic energy distribution consistent with dissociation on a ground electronic state. Similar dynamics were not observed at hν = 4.66 eV even though there is clear evidence for recovery of the ground electronic state of [C7H9–CO2]−. In accord with supporting electronic structure calculations, the production of H– at hν = 4.13 eV is explained by excited-state dissociation of CO2 to form [C7H9]−, which subsequently undergoes a ring-closure isomerization reaction to yield toluene and H–. These data represent the first evidence for a photoinduced ring-closing isomerization reaction in an anionic polyene and provides an interesting example of the rich anion dynamics that can occur in the detachment continuum and that can influence photochemistry. |
| Databáze: | OpenAIRE |
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