% IMPORTANT: The following is UTF-8 encoded.  This means that in the presence
% of non-ASCII characters, it will not work with BibTeX 0.99 or older.
% Instead, you should use an up-to-date BibTeX implementation like “bibtex8” or
% “biber”.

@ARTICLE{Thompson:639396,
      author       = {Thompson, Henry J. and Bonanomi, Matteo and Pedersen, Jacob
                      and Plekan, Oksana and Pal, Nitish and Grazioli, Cesare and
                      Prince, Kevin C. and Tenorio, Bruno N. C. and Devetta,
                      Michele and Faccialà, Davide and Vozzi, Caterina and
                      Piseri, Paolo and Danailov, Miltcho B. and Demidovich,
                      Alexander and Brynes, Alexander D. and Simoncig, Alberto and
                      Zangrando, Marco and Coreno, Marcello and Feifel, Raimund
                      and Squibb, Richard J. and Holland, David M. P. and Allum,
                      Felix and Rolles, Daniel and Decleva, Piero and Schuurman,
                      Michael S. and Forbes, Ruaridh and Coriani, Sonia and
                      Callegari, Carlo and Minns, Russell S. and Di Fraia,
                      Michele},
      title        = {{S}hake-{D}own {S}pectroscopy as {S}tate- and
                      {S}ite-{S}pecific {P}robe of {U}ltrafast {C}hemical
                      {D}ynamics},
      journal      = {Journal of the American Chemical Society},
      volume       = {147},
      number       = {36},
      issn         = {0002-7863},
      address      = {Washington, DC},
      publisher    = {ACS Publications},
      reportid     = {PUBDB-2025-04490},
      pages        = {32851 - 32860},
      year         = {2025},
      note         = {CUI: Advanced Imaging of Matter},
      abstract     = {Tracking the multifarious ultrafast electronic and
                      structural changes occurring in a molecule during a
                      photochemical transformation is a challenging endeavor that
                      benefits from recent experimental and computational progress
                      in time-resolved techniques. Measurements of valence
                      electronic states, which provide a global picture of the
                      bonding structure of the molecule, and core electronic
                      states, which provide insight into the local environment,
                      traditionally require different approaches and are often
                      studied separately. Here, we demonstrate that X-ray pulses
                      from a seeded free-electron laser (FEL) enable the
                      measurement of high-resolution, time-resolved X-ray
                      photoelectron spectra (XPS) that capture weak satellite
                      states resulting from shake-down processes in a
                      valence-excited molecule. This approach effectively combines
                      the advantages of both valence- and core-state
                      investigations. We applied this method to investigate
                      photoexcited CS2 molecules, where the role of internal
                      conversion (IC) and intersystem crossing (ISC) in
                      determining the predissociation dynamics is controversial.
                      We present XPS spectra from photoexcited CS2, obtained at
                      the FERMI FEL. High-resolution measurements, compared to the
                      corresponding spectra obtained from accurate multireference
                      quantum chemical calculations, reveal that shake-down
                      satellite channels are highly sensitive to both valence
                      electronic and geometric changes. Previous studies of the
                      predissociation dynamics have led to uncertain assignments
                      of the branching between singlet and triplet excited states.
                      We derive a propensity rule that demonstrates the
                      spin-selectivity of the shake-downs. This selectivity allows
                      us to unequivocally assign contributions from the bright and
                      dark singlet excited states, with populations tracked along
                      the predissociation dynamic pathway.},
      cin          = {CFEL-DESYT},
      ddc          = {540},
      cid          = {I:(DE-H253)CFEL-DESYT-20160930},
      pnm          = {631 - Matter – Dynamics, Mechanisms and Control
                      (POF4-631) / Ex-Net-0002-Phase2-3 - Advanced Imaging of
                      Matter: Structure, Dynamics and Control on the Atomic Scale
                      - AIM $(2018_Ex-Net-0002-Phase2-3)$},
      pid          = {G:(DE-HGF)POF4-631 / $G:(DE-HGF)2018_Ex-Net-0002-Phase2-3$},
      experiment   = {EXP:(DE-MLZ)NOSPEC-20140101},
      typ          = {PUB:(DE-HGF)16},
      doi          = {10.1021/jacs.5c09162},
      url          = {https://bib-pubdb1.desy.de/record/639396},
}