Time-resolved inner-shell photoelectron spectroscopy: From a bound molecule to an isolated atom

Felix Brausse (1) , Gildas Goldsztejn (1) , Kasra Amini (2) , Rebecca Boll (3) , Sadia Bari (3) , Cédric Bomme (3) , Mark Brouard (2) , Michael Burt (2) , Barbara Cunha de Miranda (4) , Stefan Düsterer (3) , Benjamin Erk (3) , Marie Géléoc (5, 6) , Romain Géneaux (5, 7) , Alexander Gentleman (2) , Renaud Guillemin (4) , Iyas Ismail (4) , Per Johnsson (8) , Loïc Journel (4) , Thomas Kierspel (9, 10) , Hansjochen Köckert (2) , Jochen Küpper (9, 10) , Pascal Lablanquie (4) , Jan Lahl (8) , Jason Lee (2) , Stuart Mackenzie (2) , Sylvain Maclot (8) , Bastian Manschwetus (3) , Andrey Mereshchenko (11) , Terence Mullins (9) , Pavel Olshin (11) , Jerome Palaudoux (4) , Serguei Patchkovskii (1) , Francis Penent (4, 12) , Maria Novella Piancastelli (4, 12) , Dimitrios Rompotis (3) , Thierry Ruchon (5, 7) , Artem Rudenko (13) , Evgeny Savelyev (3) , Nora Schirmel (3) , Simone Simon (3, 14) , Oksana Travnikova (4) , Sebastian Trippel (9, 10) , Jonathan Underwood (15) , Claire Vallance (2) , Joss Wiese (9) , Marc Simon (4) , David Holland , Tatiana Marchenko (4) , Arnaud A. Rouzée (1) , Daniel Rolles (13)

1 MBI - Max-Born-Institut für Nichtlineare Optik und Kurzzeitspektroskopie
2 University of Oxford
3 DESY - Deutsches Elektronen-Synchrotron [Hamburg]
4 LCPMR - Laboratoire de Chimie Physique - Matière et Rayonnement
5 LIDyl - Laboratoire Interactions, Dynamiques et Lasers (ex SPAM)
6 SBM - Structures BioMoléculaires
7 ATTO - Attophysique
8 Lund University [Lund]
9 CFEL - Center for Free-Electron Laser Science
10 UHH - Universität Hamburg
11 SPSPU - Saint Petersburg State Polytechnical University
12 Department of Physics and Astronomy [Uppsala]
13 Kansas State University
14 Max-Planck-Institut für Biophysikalische Chemie - Max Planck Institute for Biophysical Chemistry [Göttingen]
15 Department of Physics and Astronomy [UCL London]

Due to its element and site specificity, inner-shell photoelectron spectroscopy is a widely used technique to probe the chemical structure of matter. Here, we show that time-resolved inner-shell photoelectron spectroscopy can be employed to observe ultrafast chemical reactions and the electronic response to the nuclear motion with high sensitivity. The ultraviolet dissociation of iodomethane (CH3I) is investigated by ionization above the iodine 4d edge, using time-resolved inner-shell photoelectron and photoion spectroscopy. The dynamics observed in the photoelectron spectra appear earlier and are faster than those seen in the iodine fragments. The experimental results are interpreted using crystal-field and spin-orbit configuration interaction calculations, and demonstrate that time-resolved inner-shell photoelectron spectroscopy is a powerful tool to directly track ultrafast structural and electronic transformations in gas-phase molecules.

Domains: Theoretical and/or physical chemistry; Chemical Physics [physics.chem-ph]

Felix Brausse, Gildas Goldsztejn, Kasra Amini, Rebecca Boll, Sadia Bari, et al.. Time-resolved inner-shell photoelectron spectroscopy: From a bound molecule to an isolated atom. Physical Review A : Atomic, molecular, and optical physics [1990-2015], 2018, 97 (4), ⟨10.1103/PhysRevA.97.043429⟩. ⟨cea-01894499⟩