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

Abstract

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.

References in corpus (3)

• Diffractive Imaging of Coherent Nuclear Motion in Isolated Molecules
• Self-referenced coherent diffraction x-ray movie of Angstrom- and femtosecond-scale atomic motion
• Time-resolved photoelectron spectroscopy of non-adiabatic dynamics in polyatomic molecules

Cited by in corpus (8)

• Following excited-state chemical shifts in molecular ultrafast x-ray photoelectron spectroscopy
• Probing the UV-Induced Photodissociation of CH${}_{\text{3}}$I and C${}_{\text{6}}$H${}_{\text{3}}$F${}_{\text{2}}$I with Femtosecond Time-Resolved Coulomb Explosion Imaging at FLASH
• Spectroscopic Signature of Chemical Bond Dissociation Revealed by Calculated Core-Electron Spectra
• Transient Resonant Auger-Meitner Spectra of Photoexcited Thymine
• Unraveling the relaxation dynamics of Uracil: insights from time-resolved X-ray photoelectron spectroscopy
• Shake-down spectroscopy as state- and site-specific probe of ultrafast chemical dynamics
• Photon Energy-Resolved Velocity Map Imaging from Spectral Domain Ghost Imaging
• Photoinduced enhancement of chemical shift sensitivity to local vibrations