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Charged particle imaging of the deprotonated octatrienoic acid anion : evidence for a photoinduced cyclization reaction.

West, C.W. and Bull, J.N. and 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). pp. 4635-4640.

Abstract

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.

Item Type:Article
Full text:(AM) Accepted Manuscript
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Status:Peer-reviewed
Publisher Web site:https://doi.org/10.1021/acs.jpclett.6b02302
Publisher statement:This document is the Accepted Manuscript version of a Published Work that appeared in final form in The journal of physical chemistry letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpclett.6b02302
Date accepted:03 November 2016
Date deposited:24 November 2016
Date of first online publication:03 November 2016
Date first made open access:03 November 2017

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