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The nonlinear interaction of x-rays with matter is at the heart of understanding and controlling ultrafast molecular dynamics from an atom-specific viewpoint, providing new scientific and analytical opportunities to explore the structure and dynamics of small quantum systems. At increasingly high x-ray intensity, the sensitivity of ultrashort x-ray pulses to specific electronic states and emerging short-lived transient intermediates is of particular relevance for our understanding of fundamental multi-photon absorption processes. In this work, intense x-ray free-electron laser (XFEL) pulses at the European XFEL (EuXFEL) are combined with a gas cell and grating spectrometer for a high-intensity transmission spectroscopy study of multiphoton-induced ultrafast molecular fragmentation dynamics in CF$_4$. This approach unlocks the direct intra-pulse observation of transient fragments, including neutral atoms, by their characteristic absorption lines in the transmitted broad-band x-ray spectrum. The dynamics with and without initially producing fluorine K-shell holes are studied by tuning the central photon energy. The absorption spectra are measured at different FEL intensities to observe nonlinear effects. Transient isolated fluorine atoms and ions are spectroscopically recorded within the ultrashort pulse duration of few tens of femtoseconds. An isosbestic point that signifies the correlated transition between intact neutral CF$_4$ molecules and charged atomic fragments is observed near the fluorine K-edge. The dissociation dynamics and the multiphoton absorption-induced dynamics encoded in the spectra are theoretically interpreted. Overall, this study demonstrates the potential of high-intensity x-ray transmission spectroscopy to study ultrafast molecular dynamics with sensitivity to specific intermediate species and their electronic structure., Comment: 30 pages, with 7 figures, submitted to Phys. Rev. X

Molecular photoabsorption results in an electronic excitation/ionization which couples to the rearrangement of the nuclei. The resulting intertwined change of nuclear and electronic degrees of freedom determines the conversion of photoenergy into other molecular energy forms. Nucleobases are excellent candidates for studying such dynamics, and great effort has been taken in the past to observe the electronic changes induced by the initial excitation in a time-resolved manner using ultrafast electron spectroscopy. The linked geometrical changes during nucleobase photorelaxation have so far not been observed directly in time-resolved experiments. Here, we present a study on a thionucleobase, where we extract comprehensive information on the molecular rearrangement using Coulomb explosion imaging. Our measurement links the extracted deplanarization of the molecular geometry to the previously studied temporal evolution of the electronic properties of the system. In particular, the protons of the exploded molecule are well-suited messengers carrying rich information on the molecule's geometry at distinct times after the initial electronic excitation. The combination of ultrashort laser pulses to trigger molecular dynamics, intense X-ray free-electron laser pulses for the explosion of the molecule, and multi-particle coincidence detection opens new avenues for time-resolved studies of complex molecules in the gas phase., Comment: 19 pages, 8 figures

A permanently available molecular-beam injection setup for controlled molecules (COMO) was installed and commissioned at the small quantum systems (SQS) instrument at the European x-ray free-electron laser (EuXFEL). A $b$-type electrostatic deflector allows for pure state-, size-, and isomer-selected samples of polar molecules and clusters. The source provides a rotationally cold ($T\approx1$~K) and dense ($\rho\approx10^8$~cm$^{-3}$) molecular beam with pulse durations up to 100~\us generated by a new version of the Even-Lavie valve. Here, a performance overview of the COMO setup is presented along with characterization experiments performed both, with an optical laser at the Center for Free-Electron-Laser Science and with x-rays at EuXFEL under burst-mode operation. COMO was designed to be attached to different instruments at the EuXFEL, in particular at the small quantum systems (SQS) and single particles, clusters, and biomolecules (SPB) instruments. This advanced controlled-molecules injection setup enables XFEL studies using highly defined samples with soft and hard x-ray FEL radiation for applications ranging from atomic, molecular, and cluster physics to elementary processes in chemistry and biology.

Double-core-hole (DCH) states in isolated water and heavy water molecules, resulting from the sequential absorption of two x-ray photons, have been investigated. A comparison of the subsequent Auger emission spectra from the two isotopes provides direct evidence of ultrafast nuclear motion during the 1.5 fs lifetime of these DCH states. Our numerical results align well with the experimental data, providing for various DCH states an in-depth study of the dynamics responsible of the observed isotope effect.

Superfluid helium nanodroplets are an ideal environment for the formation of metastable, self-organized dopant nanostructures. However, the presence of vortices often hinders their formation. Here, we demonstrate the generation of vortex-free helium nanodroplets and explore the size range in which they can be produced. From x-ray diffraction images of xenon-doped droplets, we identify that single compact structures, assigned to vortex-free aggregation, prevail up to $10^8$ atoms per droplet. This finding builds the basis for exploring the assembly of far-from-equilibrium nanostructures at low temperatures., Comment: main article: 7 pages, 3 figures; supplementary material: 12 pages, 8 figures

We have explored the light induced dynamics in superfluid helium nanodroplets with wide-angle scattering in a pump-probe measurement scheme. The droplets are doped with xenon atoms to facilitate the ignition of a nanoplasma through irradiation with near-infrared laser pulses. After a variable time delay of up to 800 ps, we image the subsequent dynamics using intense extreme ultraviolet pulses from the FERMI free-electron laser. The recorded scattering images exhibit complex intensity fluctuations that are categorized based on their characteristic features. Systematic simulations of wide-angle diffraction patterns are performed, which can qualitatively explain the observed features by employing model shapes with both randomly distributed as well as structured, symmetric distortions. This points to a connection between the dynamics and the positions of the dopants in the droplets. In particular, the structured fluctuations might be governed by an underlying array of quantized vortices in the superfluid droplet as has been observed in previous small-angle diffraction experiments. Our results provide a basis for further investigations of dopant-droplet interactions and associated heating mechanisms., Comment: 24 pages, 8 figures, 1 table

Here, we report on the nonlinear ionization of argon atoms in the short wavelength regime using ultraintense x rays from the European XFEL. After sequential multiphoton ionization, high charge states are obtained. For photon energies that are insufficient to directly ionize a $1s$ electron, a different mechanism is required to obtain ionization to Ar$^{17+}$. We propose this occurs through a two-color process where the second harmonic of the FEL pulse resonantly excites the system via a $1s \rightarrow 2p$ transition followed by ionization by the fundamental FEL pulse, which is a type of x-ray resonance-enhanced multiphoton ionization (REMPI). This resonant phenomenon occurs not only for Ar$^{16+}$, but through multiple lower charge states, where multiple ionization competes with decay lifetimes, making x-ray REMPI distinctive from conventional REMPI. With the aid of state-of-the-art theoretical calculations, we explain the effects of x-ray REMPI on the relevant ion yields and spectral profile., Comment: 8 pages, 5 figures, one supplementary material (not included)

The X-ray free-electron lasers that became available during the last decade, like the European XFEL (EuXFEL), place high demands on their instrumentation. Especially at low photon energies below $1\,\text{keV}$, detectors with high sensitivity, and consequently low noise and high quantum efficiency, are required to enable facility users to fully exploit the scientific potential of the photon source. A 1-Megapixel pnCCD detector with a $1024\times 1024$ pixel format has been installed and commissioned for imaging applications at the Nano-Sized Quantum System (NQS) station of the Small Quantum System (SQS) instrument at EuXFEL. The instrument is currently operating in the energy range between $0.5$ and $3\,\text{keV}$ and the NQS station is designed for investigations of the interaction of intense FEL pulses with clusters, nano-particles and small bio-molecules, by combining photo-ion and photo-electron spectroscopy with coherent diffraction imaging techniques. The core of the imaging detector is a pn-type charge coupled device (pnCCD) with a pixel pitch of $75\,\mu\text{m}\times 75\,\mu\text{m}$. Depending on the experimental scenario, the pnCCD enables imaging of single photons thanks to its very low electronic noise of $3$e$^-$ and high quantum efficiency. Here we present an overview on the EuXFEL pnCCD detector and the results from the commissioning and first user operation at the SQS experiment in June 2019. The detailed descriptions of the detector design and capabilities, its implementation at EuXFEL both mechanically and from the controls side as well as important data correction steps aim to provide useful background for users planning and analyzing experiments at EuXFEL and may serve as a benchmark for comparing and planning future endstations at other FELs., Comment: 10 pages, 10 figures, submitted to the Journal of Synchrotron Radiation

Intense short-wavelength pulses from free-electron lasers and high-harmonic-generation sources enable diffractive imaging of individual nano-sized objects with a single x-ray laser shot. The enormous data sets with up to several million diffraction patterns represent a severe problem for data analysis, due to the high dimensionality of imaging data. Feature recognition and selection is a crucial step to reduce the dimensionality. Usually, custom-made algorithms are developed at a considerable effort to approximate the particular features connected to an individual specimen, but facing different experimental conditions, these approaches do not generalize well. On the other hand, deep neural networks are the principal instrument for today's revolution in automated image recognition, a development that has not been adapted to its full potential for data analysis in science. We recently published in Langbehn et al. (Phys. Rev. Lett. 121, 255301 (2018)) the first application of a deep neural network as a feature extractor for wide-angle diffraction images of helium nanodroplets. Here we present the setup, our modifications and the training process of the deep neural network for diffraction image classification and its systematic benchmarking. We find that deep neural networks significantly outperform previous attempts for sorting and classifying complex diffraction patterns and are a significant improvement for the much-needed assistance during post-processing of large amounts of experimental coherent diffraction imaging data., Comment: Published Version. Github code available at: https://github.com/julian-carpenter/airynet

A significant fraction of superfluid helium nanodroplets produced in a free-jet expansion have been observed to gain high angular momentum resulting in large centrifugal deformation. We measured single-shot diffraction patterns of individual rotating helium nanodroplets up to large scattering angles using intense extreme ultraviolet light pulses from the FERMI free-electron laser. Distinct asymmetric features in the wide-angle diffraction patterns enable the unique and systematic identification of the three-dimensional droplet shapes. The analysis of a large dataset allows us to follow the evolution from axisymmetric oblate to triaxial prolate and two-lobed droplets. We find that the shapes of spinning superfluid helium droplets exhibit the same stages as classical rotating droplets while the previously reported metastable, oblate shapes of quantum droplets are not observed. Our three-dimensional analysis represents a valuable landmark for clarifying the interrelation between morphology and superfluidity on the nanometer scale.

We have recorded the coherent diffraction images of individual xenon clusters with intense extreme ultraviolet pulses to elucidate the influence of light-induced electronic changes on the diffraction pattern. Using the FLASH free-electron laser we tuned the wavelength to specific xenon atomic and ionic resonances. The data show the emergence of a transient core-shell structure within the otherwise homogeneous sample. Simulations indicate that ionization and nanoplasma formation result in a cluster shell with strongly altered refraction. The presented resonant scattering approach enables imaging of ultrafast electron dynamics on their natural time scale.

Coherent diffractive imaging of individual free nanoparticles has opened novel routes for the in-situ analysis of their transient structural, optical, and electronic properties. So far, single-shot single-particle diffraction was assumed to be feasible only at extreme ultraviolet (XUV) and X-ray free-electron lasers, restricting this research field to large-scale facilities. Here we demonstrate single-shot imaging of isolated helium nanodroplets using XUV pulses from a femtosecond-laser driven high harmonic source. We obtain bright wide-angle scattering patterns, that allow us to uniquely identify hitherto unresolved prolate shapes of superfluid helium droplets. Our results mark the advent of single-shot gas-phase nanoscopy with lab-based short-wavelength pulses and pave the way to ultrafast coherent diffractive imaging with phase-controlled multicolor fields and attosecond pulses.