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Unraveling the decarboxylation dynamics of the fluorescein dianion with fragment action spectroscopy

Gibbard, J.A.; Verlet, J.R.R.

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Authors

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Dr Jemma Gibbard jemma.gibbard@durham.ac.uk
Royal Society University Research Fellow



Abstract

The decarboxylation dynamics of the doubly deprotonated fluorescein dianion, Fl2−, are investigated by recording fragment action spectra for the anion, Fl−, and its decarboxylated analog, Fl–CO2−, using a new reflectron secondary mass spectrometer. The formation of the anion, Fl−, is directly investigated by photoelectron imaging. The Fl− and Fl–CO2− action spectra indicate that, for λ < 400 nm, one-photon dissociative photodetachment, i.e., simultaneous decarboxylation and electron loss, competes with photodetachment, whereas for λ > 400 nm, decarboxylation only proceeds following electron loss via a sequential two-photon process. The primary decarboxylation pathway is the ready loss of CO2 from the relatively short-lived intermediate excited state, Fl−[D1], which is formed by electron loss from the dianion via resonant tunneling through the repulsive Coloumb barrier associated with a high-lying excited dianion state, Fl2−[S2].

Citation

Gibbard, J., & Verlet, J. (2023). Unraveling the decarboxylation dynamics of the fluorescein dianion with fragment action spectroscopy. The Journal of Chemical Physics, 158(15), Article 154306. https://doi.org/10.1063/5.0144851

Journal Article Type Article
Acceptance Date Apr 6, 2023
Online Publication Date Apr 21, 2023
Publication Date Apr 21, 2023
Deposit Date Apr 26, 2023
Publicly Available Date Apr 26, 2023
Journal The Journal of Chemical Physics
Print ISSN 0021-9606
Electronic ISSN 1089-7690
Publisher American Institute of Physics
Peer Reviewed Peer Reviewed
Volume 158
Issue 15
Article Number 154306
DOI https://doi.org/10.1063/5.0144851

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Copyright Statement
This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Gibbard, J. A. & Verlet, J. R. R. (2023). Unraveling the decarboxylation dynamics of the fluorescein dianion with fragment action spectroscopy. The Journal of Chemical Physics 158(15): 154306 and may be found at https://doi.org/10.1063/5.0144851




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