Following excited-state chemical shifts in molecular ultrafast x-ray photoelectron spectroscopy.
Journal
Nature communications
ISSN: 2041-1723
Titre abrégé: Nat Commun
Pays: England
ID NLM: 101528555
Informations de publication
Date de publication:
11 01 2022
11 01 2022
Historique:
received:
08
08
2021
accepted:
20
12
2021
entrez:
12
1
2022
pubmed:
13
1
2022
medline:
13
1
2022
Statut:
epublish
Résumé
The conversion of photon energy into other energetic forms in molecules is accompanied by charge moving on ultrafast timescales. We directly observe the charge motion at a specific site in an electronically excited molecule using time-resolved x-ray photoelectron spectroscopy (TR-XPS). We extend the concept of static chemical shift from conventional XPS by the excited-state chemical shift (ESCS), which is connected to the charge in the framework of a potential model. This allows us to invert TR-XPS spectra to the dynamic charge at a specific atom. We demonstrate the power of TR-XPS by using sulphur 2p-core-electron-emission probing to study the UV-excited dynamics of 2-thiouracil. The method allows us to discover that a major part of the population relaxes to the molecular ground state within 220-250 fs. In addition, a 250-fs oscillation, visible in the kinetic energy of the TR-XPS, reveals a coherent exchange of population among electronic states.
Identifiants
pubmed: 35017539
doi: 10.1038/s41467-021-27908-y
pii: 10.1038/s41467-021-27908-y
pmc: PMC8752854
doi:
Types de publication
Journal Article
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.
Langues
eng
Sous-ensembles de citation
IM
Pagination
198Commentaires et corrections
Type : ErratumIn
Informations de copyright
© 2022. The Author(s).
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