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Ultrafast valence to non-valence excited state dynamics in a common anionic chromophore

Bull, James N.; Anstöter, Cate S.; Verlet, Jan R.R.

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Authors

James N. Bull

Cate S. Anstöter



Abstract

Non-valence states in neutral molecules (Rydberg states) have well-established roles and importance in photochemistry, however, considerably less is known about the role of non-valence states in photo-induced processes in anions. Here, femtosecond time-resolved photoelectron imaging is used to show that photoexcitation of the S1(ππ*) state of the methyl ester of deprotonated para-coumaric acid – a model chromophore for photoactive yellow protein (PYP) – leads to a bifurcation of the excited state wavepacket. One part remains on the S1(ππ*) state forming a twisted intermediate, whilst a second part leads to the formation of a non-valence (dipole-bound) state. Both populations eventually decay independently by vibrational autodetachment. Valence-to-non-valence internal conversion has hitherto not been observed in the intramolecular photophysics of an isolated anion, raising questions into how common such processes might be, given that many anionic chromophores have bright valence states near the detachment threshold.

Citation

Bull, J. N., Anstöter, C. S., & Verlet, J. R. (2019). Ultrafast valence to non-valence excited state dynamics in a common anionic chromophore. Nature Communications, 10(1), Article 5820. https://doi.org/10.1038/s41467-019-13819-6

Journal Article Type Article
Acceptance Date Nov 27, 2019
Online Publication Date Dec 20, 2019
Publication Date Dec 20, 2019
Deposit Date Jan 2, 2020
Publicly Available Date Mar 29, 2024
Journal Nature Communications
Publisher Nature Research
Peer Reviewed Peer Reviewed
Volume 10
Issue 1
Article Number 5820
DOI https://doi.org/10.1038/s41467-019-13819-6

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http://creativecommons.org/licenses/by/4.0/

Copyright Statement
Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.





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