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Durham University

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Publication details for Prof. Jan R.R. Verlet

West, C.W., Bull, J.N. & Verlet, J.R.R. (2016). Charged Particle Imaging of the Deprotonated Octatrienoic Acid Anion: Evidence for a Photoinduced Cyclization Reaction. The Journal of Physical Chemistry Letters 7(22): 4635-4640.

Author(s) from Durham


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.