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

• Published in: arXiv.org
• Main Authors: Brauße, Felix, Goldsztejn, Gildas, Amini, Kasra, Boll, Rebecca, Bari, Sadia, Bomme, Cédric, Brouard, Mark, Burt, Michael, Cunha de Miranda, Barbara, Düsterer, Stefan, Erk, Benjamin, Géléoc, Marie, Geneaux, Romain, Gentleman, Alexander S, Guillemin, Renaud, Ismail, Iyas, Johnsson, Per, Journel, Loïc, Kierspel, Thomas, Köckert, Hansjochen, Küpper, Jochen, Lablanquie, Pascal, Lahl, Jan, Lee, Jason W L, Mackenzie, Stuart R, Maclot, Sylvain, Manschwetus, Bastian, Mereshchenko, Andrey S, Mullins, Terence, Olshin, Pavel K, Palaudoux, Jérôme, Patchkovskii, Serguei, Penent, Francis, Maria Novella Piancastelli, Rompotis, Dimitrios, Ruchon, Thierry, Rudenko, Artem, Savelyev, Evgeny, Schirmel, Nora, Techert, Simone, Travnikova, Oksana, Trippel, Sebastian, Underwood, Jonathan G, Vallance, Claire, Wiese, Joss, Simon, Marc, Holland, David M P, Marchenko, Tatiana, Rouzée, Arnaud, Rolles, Daniel
• Format: Paper Journal Article
• Language: English
• Published: Ithaca Cornell University Library, arXiv.org 25.01.2019
• Subjects: Chemical reactions; Configuration interaction; Electrons; Iodine; Ionization; Ions; Nuclear reactions; Organic chemistry; Phase transitions; Photoelectron spectroscopy; Photoelectrons; Physics - Chemical Physics; Spectrum analysis
• ISSN: 2331-8422
• DOI: 10.48550/arxiv.1901.08937

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 (CH\(_3\)I) 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.