Experimental Realization of Auger Decay in the Field of a Positive Elementary Charge.

Auger electron spectroscopy is an omnipresent experimental tool in many fields of fundamental research and applied science. The determination of the kinetic energies of the Auger electrons yields information about the element emitting the electron and its chemical environment at the time of emission. Here, we present an experimental approach to determine Auger spectra for emitter sites in the vicinity of a positive elementary charge based on electron-electron-electron and electron-electron-photon coincidence spectroscopy. We observe a characteristic redshift of the Auger spectrum caused by the Coulomb interaction with the charged environment. Our results are relevant for the interpretation of Auger spectra of extended systems like large molecules, clusters, liquids, and solids, in particular in high-intensity radiation fields which are nowadays routinely available, e.g., at x-ray free-electron laser facilities. The effect has been widely ignored in the literature so far, and some interpretations of Auger spectra from clusters might need to be revisited.

X-ray radiation damage cycle of solvated inorganic ions.

X-ray-induced damage is one of the key topics in radiation chemistry. Substantial damage is attributed to low-energy electrons and radicals emerging from direct inner-shell photoionization or produced by subsequent processes. We apply multi-electron coincidence spectroscopy to X-ray-irradiated aqueous solutions of inorganic ions to investigate the production of low-energy electrons (LEEs) in a predicted cascade of intermolecular charge- and energy-transfer processes, namely electron-transfer-mediated decay (ETMD) and interatomic/intermolecular Coulombic decay (ICD). An advanced coincidence technique allows us to identify several LEE-producing steps during the decay of 1s vacancies in solvated Mg2+ ions, which escaped observation in previous non-coincident experiments. We provide strong evidence for the predicted recovering of the ion's initial state. In natural environments the recovering of the ion's initial state is expected to cause inorganic ions to be radiation-damage hot spots, repeatedly producing destructive particles under continuous irradiation.

Artificial intelligence for online characterization of ultrashort X-ray free-electron laser pulses.

X-ray free-electron lasers (XFELs) as the world's brightest light sources provide ultrashort X-ray pulses with a duration typically in the order of femtoseconds. Recently, they have approached and entered the attosecond regime, which holds new promises for single-molecule imaging and studying nonlinear and ultrafast phenomena such as localized electron dynamics. The technological evolution of XFELs toward well-controllable light sources for precise metrology of ultrafast processes has been, however, hampered by the diagnostic capabilities for characterizing X-ray pulses at the attosecond frontier. In this regard, the spectroscopic technique of photoelectron angular streaking has successfully proven how to non-destructively retrieve the exact time-energy structure of XFEL pulses on a single-shot basis. By using artificial intelligence techniques, in particular convolutional neural networks, we here show how this technique can be leveraged from its proof-of-principle stage toward routine diagnostics even at high-repetition-rate XFELs, thus enhancing and refining their scientific accessibility in all related disciplines.

A localized view on molecular dissociation via electron-ion partial covariance.

Inner-shell photoelectron spectroscopy provides an element-specific probe of molecular structure, as core-electron binding energies are sensitive to the chemical environment. Short-wavelength femtosecond light sources, such as Free-Electron Lasers (FELs), even enable time-resolved site-specific investigations of molecular photochemistry. Here, we study the ultraviolet photodissociation of the prototypical chiral molecule 1-iodo-2-methylbutane, probed by extreme-ultraviolet (XUV) pulses from the Free-electron LASer in Hamburg (FLASH) through the ultrafast evolution of the iodine 4d binding energy. Methodologically, we employ electron-ion partial covariance imaging as a technique to isolate otherwise elusive features in a two-dimensional photoelectron spectrum arising from different photofragmentation pathways. The experimental and theoretical results for the time-resolved electron spectra of the 4d3/2 and 4d5/2 atomic and molecular levels that are disentangled by this method provide a key step towards studying structural and chemical changes from a specific spectator site.

Photoelectron circular dichroism of O 1s-photoelectrons of uniaxially oriented trifluoromethyloxirane: energy dependence and sensitivity to molecular configuration.

The photoelectron circular dichroism (PECD) of the O 1s-photoelectrons of trifluoromethyloxirane (TFMOx) is studied experimentally and theoretically for different photoelectron kinetic energies. The experiments were performed employing circularly polarized synchrotron radiation and coincident electron and fragment ion detection using cold target recoil ion momentum spectroscopy. The corresponding calculations were performed by means of the single center method within the relaxed-core Hartree-Fock approximation. We concentrate on the energy dependence of the differential PECD of uniaxially oriented TFMOx molecules, which is accessible through the employed coincident detection. We also compare the results for the differential PECD of TFMOx to those obtained for the equivalent fragmentation channel and similar photoelectron kinetic energy of methyloxirane (MOx), studied in our previous work. Thereby, we investigate the influence of the substitution of the methyl group by the trifluoromethyl group at the chiral center on the molecular chiral response. Finally, the presently obtained angular distribution parameters are compared to those available in the literature.

Core and Valence Level Photoelectron Spectroscopy of Nanosolvated KCl.

The solvation of alkali and halide ions in the aqueous environment has been a subject of intense experimental and theoretical research with multidisciplinary interests; yet, a comprehensive molecular-level understanding has still not been obtained. In recent years, electron spectroscopy has been increasingly applied to study the electronic and structural properties of aqueous ions with implications, especially in atmospheric chemistry. In this work, we report core and valence level (Cl 2p, Cl 3p, and K 3p) photoelectron spectra of the common alkali halide, KCl, doped in gas-phase water clusters in the size range of a few hundred water molecules. The results indicate that the electronic structure of these nanosolutions shows a distinct character from that observed at the liquid-vapor interface in liquid microjets and ambient pressure setups. Insights are provided into the unique solvation properties of ions in a nanoaqueous environment, emerging properties of bulk electrolyte solutions with growing cluster size, and sensitivity of the electronic structure to varying solvation configurations.