Journal Article

PUBDB-2026-02384

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Photoinduced Enhancement of Chemical Shift Sensitivity to Local Vibrations

Gutiérrez, A. M. ; Alexander, O.Extern*XFEL.EU* ; Alonso, P. E. ; Paoloni, L.Extern*XFEL.EU* ; Mullins, T. ; Al-Haddad, A. ; Baumann, T.XFEL.EU* ; Boll, R.XFEL.EU* ; Bostedt, C.Extern* ; Dold, S.Extern*XFEL.EU*DESY* ; De Fanis, A.XFEL.EU* ; Geloni, G.Extern*XFEL.EU* ; Ilchen, M.XFEL.EU*DESY* ; Ismail, I.Extern* ; Lautenschlager, B. ; Mazza, T.XFEL.EU* ; Moonshiram, D.Extern* ; Oberli, S. ; PENG, D.Extern*XFEL.EU* ; Püttner, R. ; Serkez, S.XFEL.EU* ; Simon, M.Extern*XFEL.EU* ; Trinter, F.Extern*XFEL.EU* ; Usenko, S.XFEL.EU* ; Meyer, M.XFEL.EU* ; Marangos, J. P. ; González-Vázquez, J. ; Rivas, D. (Corresponding author)XFEL.EU* ; Picón, A. (Corresponding author)

2026
ACS Publications Washington, DC

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Please use a persistent id in citations: doi:10.1021/jacs.6c06538  doi:10.3204/PUBDB-2026-02384

Abstract: The advent of novel free-electron laser sources enabling time-resolved X-ray photoelectron spectroscopy (tr-XPS) provides a unique opportunity to monitor local chemical environments in real time by measuring sub-eV shifts in core-electron binding energies. These shifts reflect the interplay between electronic excitation and nuclear motion, an interplay that remains largely unexplored. In our combined theoretical and experimental study of fluoropyridine (C5H4FN), we investigate this link by monitoring the evolving chemical environment at the N and F atomic sites as the photoexcited S1 state relaxes to the ground state via a conical intersection. We find that the F site responds primarily to vibrational relaxation, showing minimal sensitivity to the electronic excited state. In contrast, excitation to S1 induces a measurable energy shift at the N site and significantly enhances its sensitivity to local vibrations within the ring. This behavior arises from a photoinduced redistribution of charge, which also increases the Coulomb interaction between the 1s electron at the N atom and the atomic partial charge at an adjacent C atom. This insight opens new avenues for exploring ultrafast dynamics and conical intersection pathways in more complex systems, from photostable DNA bases to light-harvesting materials.

Note: Open Access

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Contributing Institute(s):

1. FLASH Photonen-Diagnose und Steuerungen (FS-FLASH-D)
2. SQS (XFEL_E2_SQS)

Research Program(s):

1. 631 - Matter – Dynamics, Mechanisms and Control (POF4-631) (POF4-631)
2. DFG project G:(GEPRIS)170620586 - SFB 925: Licht-induzierte Dynamik und Kontrolle korrelierter Quantensysteme (170620586) (170620586)
3. DFG project G:(GEPRIS)390715994 - EXC 2056: CUI: Tiefe Einblicke in Materie (390715994) (390715994)
4. DFG project G:(GEPRIS)328961117 - SFB 1319: Extremes Licht zur Analyse und Kontrolle molekularer Chiralität (ELCH) (328961117) (328961117)
5. DFG project G:(GEPRIS)509471550 - Dynamik photoionisations-induzierter Prozesse in laser-präparierten Molekülen in der Gasphase und der wässrigen Phase (509471550) (509471550)

Experiment(s):

1. SQS: Small Quantum Systems (SASE3)

Appears in the scientific report 2026

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Database coverage:
; ; ; BIOSIS Previews ; Biological Abstracts ; Chemical Reactions ; Clarivate Analytics Master Journal List ; Current Contents - Life Sciences ; Current Contents - Physical, Chemical and Earth Sciences ; Ebsco Academic Search ; Essential Science Indicators ; IF >= 15 ; Index Chemicus ; JCR ; Nationallizenz ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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