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Ultrafast above-threshold dynamics of the radical anion of a prototypical quinone electron-acceptor

Horke, D.A.; Li, Q.; Blancafort, L.; Verlet, J.R.R.

Ultrafast above-threshold dynamics of the radical anion of a prototypical quinone electron-acceptor Thumbnail


Authors

D.A. Horke

Q. Li

L. Blancafort



Abstract

Quinones feature prominently as electron acceptors in nature. Their electron-transfer reactions are often highly exergonic, for which Marcus theory predicts reduced electron-transfer rates because of a free-energy barrier that occurs in the inverted region. However, the electron-transfer kinetics that involve quinones can appear barrierless. Here, we consider the intrinsic properties of the para-benzoquinone radical anion, which serves as the prototypical electron-transfer reaction product involving a quinone-based acceptor. Using time-resolved photoelectron spectroscopy and ab initio calculations, we show that excitation at 400 and 480 nm yields excited states that are unbound with respect to electron loss. These excited states are shown to decay on a sub-40 fs timescale through a series of conical intersections with lower-lying excited states, ultimately to form the ground anionic state and avoid autodetachment. From an isolated electron-acceptor perspective, this ultrafast stabilization mechanism accounts for the ability of para-benzoquinone to capture and retain electrons.

Citation

Horke, D., Li, Q., Blancafort, L., & Verlet, J. (2013). Ultrafast above-threshold dynamics of the radical anion of a prototypical quinone electron-acceptor. Nature Chemistry, 5(8), 711-717. https://doi.org/10.1038/nchem.1705

Journal Article Type Article
Acceptance Date Jun 4, 2013
Online Publication Date Jul 7, 2013
Publication Date Aug 1, 2013
Deposit Date Nov 7, 2013
Publicly Available Date Mar 29, 2024
Journal Nature Chemistry
Print ISSN 1755-4330
Electronic ISSN 1755-4349
Publisher Nature Research
Peer Reviewed Peer Reviewed
Volume 5
Issue 8
Pages 711-717
DOI https://doi.org/10.1038/nchem.1705

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