title: Light-Induced Radical Formation and Isomerization of an Aromatic Thiol in Solution Followed by Time-Resolved X-ray Absorption Spectroscopy at the Sulfur K-Edge.
abstract: We applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ∼70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemical reaction pathways and transient products of sulfur-containing molecules in solution.
authors.affiliation: Department of Physics, University of Hamburg and Center for Free Electron Laser Science , 22761 Hamburg, Germany.|Max Planck Institute for the Structure and Dynamics of Matter , 22761 Hamburg, Germany.
authors.forename: Miguel
authors.initials: M
authors.lastname: Ochmann
authors.affiliation: Department of Physics, University of Hamburg and Center for Free Electron Laser Science , 22761 Hamburg, Germany.
authors.forename: Inga
authors.initials: I
authors.lastname: von Ahnen
authors.affiliation: Ultrafast X-ray Science Lab, Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.
authors.forename: Amy A
authors.initials: AA
authors.lastname: Cordones
authors.affiliation: Department of Physics, University of Hamburg and Center for Free Electron Laser Science , 22761 Hamburg, Germany.|Max Planck Institute for the Structure and Dynamics of Matter , 22761 Hamburg, Germany.
authors.forename: Abid
authors.initials: A
authors.lastname: Hussain
authors.affiliation: Ultrafast X-ray Science Lab, Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.
authors.forename: Jae Hyuk
authors.initials: JH
authors.lastname: Lee
authors.affiliation: Ultrafast X-ray Science Lab, Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.|Department of Chemistry and Chemistry Institute of Functional Materials, Pusan National University , Busan 46241, South Korea.
authors.forename: Kiryong
authors.initials: K
authors.lastname: Hong
authors.affiliation: Department of Physics, University of Hamburg and Center for Free Electron Laser Science , 22761 Hamburg, Germany.|Max Planck Institute for the Structure and Dynamics of Matter , 22761 Hamburg, Germany.
authors.forename: Katrin
authors.initials: K
authors.lastname: Adamczyk
authors.affiliation: Center for Free-Electron Laser Science, DESY and The Hamburg Centre for Ultrafast Imaging , 22607 Hamburg, Germany.
authors.forename: Oriol
authors.identifier: 0000-0003-4629-414X
authors.initials: O
authors.lastname: Vendrell
authors.affiliation: Department of Chemistry and Chemistry Institute of Functional Materials, Pusan National University , Busan 46241, South Korea.
authors.forename: Tae Kyu
authors.identifier: 0000-0002-9578-5722
authors.initials: TK
authors.lastname: Kim
authors.affiliation: Ultrafast X-ray Science Lab, Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.
authors.forename: Robert W
authors.initials: RW
authors.lastname: Schoenlein
authors.affiliation: Department of Physics, University of Hamburg and Center for Free Electron Laser Science , 22761 Hamburg, Germany.|Max Planck Institute for the Structure and Dynamics of Matter , 22761 Hamburg, Germany.
authors.forename: Nils
authors.identifier: 0000-0002-3281-7600
authors.initials: N
authors.lastname: Huse