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DOE OSTI · 3375517

Spatial Mapping of Valence Excited-State Landscapes Using Time-Resolved Shake-Down Spectroscopy

Thompson, Henry J. [Univ. of Southampton (United Kingdom)] (ORCID:0009000727182229)·Devetta, Michele [Istituto di Fotonica e Nanotecnologie (IFN), Milan (Italy)] (ORCID:0000000238063475)·Faccialà, Davide [Istituto di Fotonica e Nanotecnologie (IFN), Milan (Italy)] (ORCID:0000000250720394)·Ingle, Rebecca A. [Univ. College London (United Kingdom)] (ORCID:0000000205663407)·Pratt, Stephen T. [Argonne National Laboratory (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division] (ORCID:0000000282821026)·Razmus, Weronika O. [Univ. of Southampton (United Kingdom)]·Vozzi, Caterina [Istituto di Fotonica e Nanotecnologie (IFN), Milan (Italy)] (ORCID:0000000202120191)·Allum, Felix [Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Institute (PULSE); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)]·Ashfold, Michael N. R. [School of Chemistry; University of Bristol] (ORCID:0000000157627048)·Coriani, Sonia [Technical Univ. of Denmark, Lyngby (Denmark)] (ORCID:000000024487897X)·Feifel, Raimund [Univ. of Gothenburg (Sweden)] (ORCID:0000000152343935)·Forbes, Ruaridh [Univ. of California, Davis, CA (United States)] (ORCID:0000000320975991)·Holland, David M. P. [Science and Technology Facilities Council (STFC), Daresbury (United Kingdom)] (ORCID:000000031351605X)·Rolles, Daniel [Kansas State Univ., Manhattan, KS (United States)] (ORCID:0000000239653477)·Squibb, Richard J. [Univ. of Gothenburg (Sweden)]·Bonanomi, Matteo [Istituto di Fotonica e Nanotecnologie (IFN), Milan (Italy); Elettra-Sincrotrone Trieste (Italy)]·Callegari, Carlo [Elettra-Sincrotrone Trieste (Italy)] (ORCID:0000000154917752)·Coreno, Marcello [Istituto di Struttura della Materia, Trieste (Italy)]·Danailov, Miltcho [Elettra-Sincrotrone Trieste (Italy)]·Demidovich, Alexander [Elettra-Sincrotrone Trieste (Italy)]·Di Fraia, Michele [Elettra-Sincrotrone Trieste (Italy); Istituto Officina dei Materiali (IOM), Trieste (Italy)] (ORCID:0000000181020799)·Grazioli, Cesare [Istituto di Struttura della Materia, Trieste (Italy)]·Manfredda, Michele [Elettra-Sincrotrone Trieste (Italy)]·Plekan, Oksana [Elettra-Sincrotrone Trieste (Italy)] (ORCID:0000000246927018)·Minns, Russell S. [Univ. of Southampton (United Kingdom)] (ORCID:0000000167752977)
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Abstract

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.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRYElectrical energyIodineIonizationKineticsX-ray photoelectron spectroscopy

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Thompson, Henry J. [Univ. of Southampton (United Kingdom)] (ORCID:0009000727182229), Devetta, Michele [Istituto di Fotonica e Nanotecnologie (IFN), Milan (Italy)] (ORCID:0000000238063475), Faccialà, Davide [Istituto di Fotonica e Nanotecnologie (IFN), Milan (Italy)] (ORCID:0000000250720394), Ingle, Rebecca A. [Univ. College London (United Kingdom)] (ORCID:0000000205663407), Pratt, Stephen T. [Argonne National Laboratory (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division] (ORCID:0000000282821026), Razmus, Weronika O. [Univ. of Southampton (United Kingdom)], Vozzi, Caterina [Istituto di Fotonica e Nanotecnologie (IFN), Milan (Italy)] (ORCID:0000000202120191), Allum, Felix [Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Institute (PULSE); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)], Ashfold, Michael N. R. [School of Chemistry; University of Bristol] (ORCID:0000000157627048), Coriani, Sonia [Technical Univ. of Denmark, Lyngby (Denmark)] (ORCID:000000024487897X), Feifel, Raimund [Univ. of Gothenburg (Sweden)] (ORCID:0000000152343935), Forbes, Ruaridh [Univ. of California, Davis, CA (United States)] (ORCID:0000000320975991), Holland, David M. P. [Science and Technology Facilities Council (STFC), Daresbury (United Kingdom)] (ORCID:000000031351605X), Rolles, Daniel [Kansas State Univ., Manhattan, KS (United States)] (ORCID:0000000239653477), Squibb, Richard J. [Univ. of Gothenburg (Sweden)], Bonanomi, Matteo [Istituto di Fotonica e Nanotecnologie (IFN), Milan (Italy); Elettra-Sincrotrone Trieste (Italy)], Callegari, Carlo [Elettra-Sincrotrone Trieste (Italy)] (ORCID:0000000154917752), Coreno, Marcello [Istituto di Struttura della Materia, Trieste (Italy)], Danailov, Miltcho [Elettra-Sincrotrone Trieste (Italy)], Demidovich, Alexander [Elettra-Sincrotrone Trieste (Italy)], Di Fraia, Michele [Elettra-Sincrotrone Trieste (Italy); Istituto Officina dei Materiali (IOM), Trieste (Italy)] (ORCID:0000000181020799), Grazioli, Cesare [Istituto di Struttura della Materia, Trieste (Italy)], Manfredda, Michele [Elettra-Sincrotrone Trieste (Italy)], Plekan, Oksana [Elettra-Sincrotrone Trieste (Italy)] (ORCID:0000000246927018), Minns, Russell S. [Univ. of Southampton (United Kingdom)] (ORCID:0000000167752977). 2026-05-22. Spatial Mapping of Valence Excited-State Landscapes Using Time-Resolved Shake-Down Spectroscopy. https://doi.org/10.1021/acs.jpca.6c02224

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