The x-ray absorption spectrum of the tert-butyl radical: An experimental and computational investigation

Dorothee Schaffner, Theo Juncker von Buchwald, Emil Karaev, Michele Alagia, Robert Richter, Stefano Stranges*, Sonia Coriani*, Ingo Fischer*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

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Abstract

We report the x-ray absorption spectrum (XAS) of the tert-butyl radical, C4H9. The radical was generated pyrolytically from azo-tert-butane, and the XAS of the pure radical was obtained by subtraction of spectra recorded at different temperatures. The bands in the XAS were assigned by ab initio calculations that are in very good agreement with the experimental data. The lowest energy signal in the XAS is assigned to the C1s electron transition from the central carbon atom to the singly occupied molecular orbital (SOMO), while higher transitions correspond to C1s excitations from terminal carbon atoms. Furthermore, we investigated the fragmentation of the radical following resonant C1s excitation by electron-ion-coincidence spectroscopy. Several fragmentation channels were identified. The C1s excitation of the terminal carbons is associated with a stronger fragmentation tendency compared to the lowest C1s excitation of the central carbon into the SOMO. For this core excited state, we still observe an intact parent ion, C4H9+, and a comparatively higher tendency to dissociate into CH3+ + C3H6+.
Original languageEnglish
Article number034309
JournalJournal of Chemical Physics
Volume161
Issue number3
Number of pages9
ISSN0021-9606
DOIs
Publication statusPublished - 2024

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