Preprint

PUBDB-2026-01122

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Unraveling Real-Time Chemical Shifts in the Ultrafast Regime

Rivas, D. (Corresponding author)XFEL.EU* ; Paoloni, L. (Corresponding author)Extern*XFEL.EU* ; Boll, R. ; De Fanis, A. ; Gutiérrez, A. M. ; Mazza, T. ; Oberli, S. ; Alexander, O. ; Al-Haddad, A. ; Baumann, T. M. ; Bostedt, C. ; Dold, S. ; Geloni, G. ; Ilchen, M.XFEL.EU*DESY* ; Moonshiram, D. ; Rolles, D.Extern* ; Rudenko, A. ; Schmidt, P. ; Serkez, S. ; Usenko, S. ; Pendás, Á. M. ; Meyer, M. ; González-Vázquez, J. ; Picón, A.Extern*XFEL.EU*

2026

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Please use a persistent id in citations: doi:10.3204/PUBDB-2026-01122

Report No.: arXiv:2512.13079

Abstract: Traditional x-ray photoelectron spectroscopy (XPS) relies upon a direct mapping between the photoelectron binding energies and the local chemical environment, which is well characterized by an electrostatic partial charges (PC) model for systems in equilibrium. However, the extension of this technique to out-of-equilibrium systems has been hampered by the lack of x-ray sources capable of accessing multiple atomic sites with high spectral and temporal resolution, as well as the lack of simple theoretical procedures to interpret the observed signals. In this work we employ XPS with a narrow band femtosecond x-ray probe to unravel different ultrafast dissociation processes of a polyatomic molecule, fluoromethane (CH3F). We demonstrate that the PC model can be successfully applied to describe the C-F and C-H dissociation dynamics after strong-field ionization, with excellent agreement between experimental measurements and ab initio simulations. These results enable the application of this technique to out-of-equilibrium systems of higher complexity, by correlating real-time information from multiple atomic sites and interpreting the measurements through a viable theoretical modeling.

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Contributing Institute(s):

1. FLASH Photonen-Diagnose und Steuerungen (FS-FLASH-D)
2. SQS (XFEL_E2_SQS)
3. FEL Physics (XFEL_E2_FP)

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)

Experiment(s):

1. XFEL Beamline SASE 3 (XFEL)

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Database coverage:
; ; Published

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Linked articles:

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Journal Article Rivas, D. (Corresponding author)XFEL.EU* ; Paoloni, L. (Corresponding author)Extern*XFEL.EU* ; Boll, R. ; De Fanis, A. ; Gutiérrez, A. M. ; Mazza, T. ; Oberli, S. ; Alexander, O. ; Al-Haddad, A. ; Baumann, T. M. ; Bostedt, C. ; Dold, S. ; Geloni, G. ; Ilchen, M.XFEL.EU*DESY* ; Moonshiram, D. ; Rolles, D.Extern* ; Rudenko, A. ; Schmidt, P. ; Serkez, S. ; Usenko, S. ; Pendás, Á. M. ; Meyer, M. ; González-Vázquez, J. ; Picón, A.Extern*XFEL.EU*
Unraveling Real-Time Chemical Shifts in the Ultrafast Regime
Physical review / X 16(1), 011051 (2026) [10.1103/y6dt-1sfw]2026     Files  Fulltext by arXiv.org BibTeX | EndNote: XML, Text | RIS

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