Spatial Mapping of Valence Excited-State Landscapes Using Time-Resolved Shake-Down Spectroscopy
Time-resolved X-ray photoelectron spectroscopy (XPS) is used to track the photodissociation dynamics of 2-iodothiophene following 262 nm excitation. The transient XPS features include both direct ionization of the initially populated excited states and pronounced satellite peaks arising from shake-down processes. While the direct ionization signals exhibit only minimal energy shifts during C-I bond cleavage, the shake-down transitions undergo a substantial, 5 eV, shift over the reaction coordinate. By correlating these shifts with simulated C-I bond lengths, a direct structural mapping is established that reveals the exceptional sensitivity of shake-down channels to molecular geometry. These results demonstrate that shake-down transitions provide a new and powerful probe of ultrafast structural dynamics.
Authors
- Oksana Plekan (ORCID: https://orcid.org/0000-0002-4692-7018)
- Felix Allum (ORCID: https://orcid.org/0000-0002-8044-8969)
- Cesare Grazioli (ORCID: https://orcid.org/0000-0002-6255-2041)
- Michele Di Fraia (ORCID: https://orcid.org/0000-0001-8102-0799)
- Michael N. R. Ashfold (ORCID: https://orcid.org/0000-0001-5762-7048)
- Michele Devetta (ORCID: https://orcid.org/0000-0002-3806-3475)
- Michele Manfredda (ORCID: https://orcid.org/0000-0002-1965-8350)
- Russell S. Minns (ORCID: https://orcid.org/0000-0001-6775-2977)
- D.M.P. Holland (ORCID: https://orcid.org/0000-0003-1351-605X)
- Henry J. Thompson (ORCID: https://orcid.org/0000-0002-3730-9322)
- M Coreno
- Davide Faccialà (ORCID: https://orcid.org/0000-0002-5072-0394)
- Sonia Coriani (ORCID: https://orcid.org/0000-0002-4487-897X)
- R. Feifel (ORCID: https://orcid.org/0000-0001-5234-3935)
- Rebecca A. Ingle (ORCID: https://orcid.org/0000-0002-0566-3407)
- S. T. Pratt (ORCID: https://orcid.org/0000-0002-8282-1026)
- Carlo Callegari (ORCID: https://orcid.org/0000-0001-5491-7752)
- Richard J. Squibb
- Alexander Demidovich
- Miltcho Danailov
- Matteo Bonanomi
- Weronika O. Razmus
- Ruaridh Forbes (ORCID: https://orcid.org/0000-0003-2097-5991)
- Daniel Rolles (ORCID: https://orcid.org/0000-0002-3965-3477)
- Caterina Vozzi (ORCID: https://orcid.org/0000-0002-0212-0191)
Institutions
- Argonne National Laboratory (US)
- Mott MacDonald (United Kingdom) (GB)
- Science and Technology Facilities Council (GB)
- Kansas State University (US)
- AREA Science Park (IT)
- Deutsches Elektronen-Synchrotron DESY (DE)
- SLAC National Accelerator Laboratory (US)
- Daresbury Laboratory (GB)
- Elettra-Sincrotrone Trieste S.C.p.A. (IT)
- University of California System (US)
- University of Bristol (GB)
- Istituto Officina dei Materiali (IT)
- Istituto di Fotonica e Nanotecnologie (IT)
- Linac Coherent Light Source (US)
- University of Southampton (GB)
- University College London (GB)
- University of Gothenburg (SE)
- Technical University of Denmark (DK)
Publication Details
- Journal
- The Journal of Physical Chemistry A
- Published
- 2026-05-22
- DOI
- https://doi.org/10.1021/acs.jpca.6c02224
- Primary Topic
- Advanced Chemical Physics Studies
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Leverhulme Trust
- University of Southampton
- Knut och Alice Wallenbergs Stiftelse
- Vetenskapsrådet
- Ministero dell'Università e della Ricerca
- Engineering and Physical Sciences Research Council
- Science and Technology Facilities Council
- Division of Physics
- Basic Energy Sciences
- Chemical Sciences, Geosciences, and Biosciences Division
- NextGenerationEU