A localized view on molecular dissociation via electron-ion partial covariance

• Main Authors: Allum, F. (Author), Bari, S. (Author), Baumann, T.M (Author), Boll, R. (Author), Brenner, G. (Author), Brouard, M. (Author), Burt, M. (Author), Demekhin, P.V (Author), Dörner, S. (Author), Ehresmann, A. (Author), Erk, B. (Author), Galler, A. (Author), Grychtol, P. (Author), Heathcote, D. (Author), Ilchen, M. (Author), Inhester, L. (Author), Kargin, D. (Author), Larsson, M. (Author), Lee, J.W.L (Author), Li, Z. (Author), Manschwetus, B. (Author), Marder, L. (Author), Mason, R. (Author), Meyer, M. (Author), Music, V. (Author), Otto, H. (Author), Passow, C. (Author), Pietschnig, R. (Author), Ramm, D. (Author), Rolles, D. (Author), Schmidt, P. (Author), Schubert, K. (Author), Schwob, L. (Author), Thomas, R.D (Author), Vallance, C. (Author), Vidanović, I. (Author), von Korff Schmising, C. (Author), Wagner, R. (Author), Walter, P. (Author), Zhaunerchyk, V. (Author)
• Format: Article
• Language: English
• Published: Nature Research 2022
• Online Access: View Fulltext in Publisher
• ISBN: 23993669 (ISSN)
• DOI: 10.1038/s42004-022-00656-w

Inner-shell photoelectron spectroscopy provides an element-specific probe of molecular structure, as core-electron binding energies are sensitive to the chemical environment. Short-wavelength femtosecond light sources, such as Free-Electron Lasers (FELs), even enable time-resolved site-specific investigations of molecular photochemistry. Here, we study the ultraviolet photodissociation of the prototypical chiral molecule 1-iodo-2-methylbutane, probed by extreme-ultraviolet (XUV) pulses from the Free-electron LASer in Hamburg (FLASH) through the ultrafast evolution of the iodine 4d binding energy. Methodologically, we employ electron-ion partial covariance imaging as a technique to isolate otherwise elusive features in a two-dimensional photoelectron spectrum arising from different photofragmentation pathways. The experimental and theoretical results for the time-resolved electron spectra of the 4d3/2 and 4d5/2 atomic and molecular levels that are disentangled by this method provide a key step towards studying structural and chemical changes from a specific spectator site. © 2022, The Author(s).