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

Bull, James N., Anstöter, Cate S. and Verlet, Jan R.R. (2019) Ultrafast valence to non-valence excited state dynamics in a common anionic chromophore. Nature Communications, 10 (1). ISSN 2041-1723

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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.

Item Type: Article
Uncontrolled Keywords: chemistry(all),biochemistry, genetics and molecular biology(all),physics and astronomy(all) ,/dk/atira/pure/subjectarea/asjc/1600
Faculty \ School: Faculty of Science > School of Chemistry
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Depositing User: LivePure Connector
Date Deposited: 03 Jan 2020 04:00
Last Modified: 16 Nov 2020 00:59
URI: https://ueaeprints.uea.ac.uk/id/eprint/73447
DOI: 10.1038/s41467-019-13819-6

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