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During the last decade, X-ray free-electron lasers (XFELs) have enabled the study of light-matter interaction under extreme conditions. Atoms which are subject to XFEL radiation are charged by a complex interplay of (several subsequent) photoionization events and electronic decay processes within a few femtoseconds. The interaction with molecules is even more intriguing, since intricate nuclear dynamics occur as the molecules start to dissociate during the charge-up process. Here, we demonstrate that by analyzing photoelectron angular emission distributions and kinetic energy release of charge states of ionic molecular fragments, we can obtain a detailed understanding of the charge-up and fragmentation dynamics. Our novel approach allows for gathering such information without the need of complex ab initio modeling. As an example, we provide a detailed view on the processes happening on a femtosecond time scale in oxygen molecules exposed to intense XFEL pulses.

The ultrafast structural dynamics of water following inner-shell ionization is a crucial issue in high-energy radiation chemistry. We have exposed isolated water molecules to a short X-ray pulse from a free-electron laser and detected momenta of all produced ions in coincidence. By combining experimental results and theoretical modeling, we can image dissociation dynamics of individual molecules in unprecedented detail. We reveal significant molecular structural dynamics in H2O2+, such as asymmetric deformation and bond-angle opening, leading to two-body or three-body fragmentation on a timescale of a few femtoseconds. We thus reconstruct several snapshots of structural dynamics at different time intervals, which highlight dynamical patterns that are relevant as initiating steps of subsequent radiation-damage processes.

A central motivation for the development of x-ray free-electron lasers has been the prospect of time-resolved single-molecule imaging with atomic resolution. Here, we show that x-ray photoelectron diffraction - where a photoelectron emitted after x-ray absorption illuminates the molecular structure from within - can be used to image the increase of the internuclear distance during the x-ray-induced fragmentation of an O2 molecule. By measuring the molecular-frame photoelectron emission patterns for a two-photon sequential K-shell ionization in coincidence with the fragment ions, and by sorting the data as a function of the measured kinetic energy release, we can resolve the elongation of the molecular bond by approximately 1.2 a.u. within the duration of the x-ray pulse. The experiment paves the road toward time-resolved pump-probe photoelectron diffraction imaging at high-repetition-rate x-ray free-electron lasers.

We investigate K-shell ionization of N2 at 40 keV photon energy. Using a cold target recoil ion momentum spectroscopy reaction microscope, we determine the vector momenta of the photoelectron, the Auger electron, and both N+ fragments. These fully differential data show that the dissociation process of the N22+ ion is significantly modified not only by the recoil momentum of the photoelectron but also by the photon momentum and the momentum of the emitted Auger electron. We find that the recoil energy introduced by the photon and the photoelectron momentum is partitioned with a ratio of approximately 30:70 between the Auger electron and fragment ion kinetic energies, respectively. We also observe that the photon momentum induces an additional rotation of the molecular ion. [ABSTRACT FROM AUTHOR]

Photoionization is one of the fundamental light-matter interaction processes in which the absorption of a photon launches the escape of an electron. The time scale of this process poses many open questions. Experiments have found time delays in the attosecond (10 -18 seconds) domain between electron ejection from different orbitals, from different electronic bands, or in different directions. Here, we demonstrate that, across a molecular orbital, the electron is not launched at the same time. Rather, the birth time depends on the travel time of the photon across the molecule, which is 247 zeptoseconds (1 zeptosecond = 10 -21 seconds) for the average bond length of molecular hydrogen. Using an electron interferometric technique, we resolve this birth time delay between electron emission from the two centers of the hydrogen molecule., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

We report on a multiparticle coincidence experiment performed at the European X-ray Free-Electron Laser at the Small Quantum Systems instrument using a COLTRIMS reaction microscope. By measuring two ions and two electrons in coincidence, we investigate double core-hole generation in O_{2} molecules in the gas phase. Single-site and two-site double core holes have been identified and their molecular-frame electron angular distributions have been obtained for a breakup of the oxygen molecule into two doubly charged ions. The measured distributions are compared to results of calculations performed within the frozen- and relaxed-core Hartree-Fock approximations.

We experimentally investigate the effects of the linear photon momentum on the momentum distributions of photoions and photoelectrons generated in one-photon ionization in an energy range of 300  eV≤E_{γ}≤40  keV. Our results show that for each ionization event the photon momentum is imparted onto the photoion, which is essentially the system's center of mass. Nevertheless, the mean value of the ion momentum distribution along the light propagation direction is backward-directed by -3/5 times the photon momentum. These results experimentally confirm a 90-year-old prediction.