Site-specific Interrogation of an Ionic Chiral Fragment During Photolysis Using an X-ray Free-Electron Laser

Abstract

Short-wavelength free-electron lasers with their ultrashort pulses at high intensities have originated new approaches for tracking molecular dynamics from the vista of specific sites. X-ray pump X-ray probe schemes even allow to address individual atomic constituents with a 'trigger'-event that preludes the subsequent molecular dynamics while being able to selectively probe the evolving structure with a time-delayed second X-ray pulse. Here, we use a linearly polarized X-ray photon to trigger the photolysis of a prototypical chiral molecule, namely trifluoromethyloxirane (C${}_3$H${}_3$F${}_3$O), at the fluorine K-edge at around 700 eV. The evolving fluorine-containing fragments are then probed by a second, circularly polarized X-ray pulse of higher photon energy in order to investigate the chemically shifted inner-shell electrons of the ionic motherfragment for their stereochemical sensitivity. We experimentally demonstrate and theoretically support how two-color X-ray pump X-ray probe experiments with polarization control enable XFELs as tools for chiral recognition.

arXiv comment14 pages, 5 figures

References in corpus (7)

• Relaxation Dynamics in Photoexcited Chiral Molecules Studied by Time-Resolved Photoelectron Circular Dichroism: Toward Chiral Femtochemistry
• Real-time probing of chirality during a chemical reaction
• Photoinduced molecular chirality probed by ultrafast resonant X-ray spectroscopy
• Emitter-site selective photoelectron circular dichroism of trifluoromethyloxirane
• Spectroscopic Signature of Chemical Bond Dissociation Revealed by Calculated Core-Electron Spectra
• Ultrafast x-ray-induced nuclear dynamics in diatomic molecules using femtosecond x-ray/x-ray pump-probe spectroscopy
• Theoretical evidence for the sensitivity of charge-rearrangement-enhanced x-ray ionization to molecular size

Cited by in corpus (7)

• Molecular chirality and its monitoring by ultrafast X-ray pulses
• Femtosecond photoelectron circular dichroism of chemical reactions
• Time-resolved chiral X-Ray photoelectron spectroscopy with transiently enhanced atomic site-selectivity: a Free Electron Laser investigation of electronically excited fenchone enantiomers
• Photoelectron circular dichroism of O 1$s$-photoelectrons of uniaxially oriented trifluoromethyloxirane: Energy dependence and sensitivity to molecular configuration
• The Time-resolved Atomic, Molecular and Optical Science Instrument at the Linac Coherent Light Source
• Circular Dichroism in Multiphoton Ionization of Resonantly Excited Helium Ions near Channel Closing
• Photon Energy-Resolved Velocity Map Imaging from Spectral Domain Ghost Imaging