Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 7, Issue 22, Pages 4635-4640Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.6b02302
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Funding
- ERC [306536]
- European Research Council (ERC) [306536] Funding Source: European Research Council (ERC)
- Engineering and Physical Sciences Research Council [1214484] Funding Source: researchfish
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Photoelectron spectroscopy of the deprotonated octatrienoic acid anion, [C7H9-CO2](-), shows the formation of [C7H9](-) and loss of H- at hv = 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 hv = 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 Hat hv = 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.
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