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We present a general experimental concept for jitter-free pump and probe experiments at free electron lasers. By generating pump and probe pulse from one and the same X-ray pulse using an optical split-and-delay unit, we obtain a temporal resolution that is limited only by the X-ray pulse lengths. In a two-color X-ray pump and X-ray probe experiment with sub 70 fs temporal resolution, we selectively probe the response of orbital and charge degree of freedom in the prototypical functional oxide magnetite after photoexcitation. We find electronic order to be quenched on a time scale of (30 ± 30) fs and hence most likely faster than what is to be expected for any lattice dynamics. Our experimental result hints to the formation of a short lived transient state with decoupled electronic and lattice degree of freedom in magnetite. The excitation and relaxation mechanism for X-ray pumping is discussed within a simple model leading to the conclusion that within the first 10 fs the original photoexcitation decays into low-energy electronic excitations comparable to what is achieved by optical pump pulse excitation. Our findings show on which time scales dynamical decoupling of degrees of freedom in functional oxides can be expected and how to probe this selectively with soft X-ray pulses. Results can be expected to provide crucial information for theories for ultrafast behavior of materials and help to develop concepts for novel switching devices.

For the European x-ray free electron laser (XFEL) a split-and-delay unit based on geometrical wavefront beam splitting and multilayer mirrors is built which covers the range of photon energies from 5 keV up to 20 keV. Maximum delays between Δτ=±2.5 ps at hν=20 keV and up to Δτ=±23 ps at hν=5 keV will be possible. Time-dependent wave-optics simulations have been performed by means of Synchrotron Radiation Workshop software for XFEL pulses at hν=5 keV. The XFEL radiation was simulated using results of time-dependent simulations applying the self-amplified spontaneous emission code FAST. Main features of the optical layout, including diffraction on the beam splitter edge and optics imperfections measured with a nanometer optic component measuring machine slope measuring profiler, were taken into account. The impact of these effects on the characterization of the temporal properties of XFEL pulses is analyzed. An approach based on fast Fourier transformation allows for the evaluation of the temporal coherence despite large wavefront distortions caused by the optics imperfections. In this way, the fringes resulting from time-dependent two-beam interference can be filtered and evaluated yielding a coherence time of τ_{c}=0.187 fs (HWHM) for real, nonperfect mirrors, while for ideal mirrors a coherence time of τ_{c}=0.191 fs (HWHM) is expected.

The average temporal (longitudinal) and spatial (transverse) coherence of free-electron-laser pulses in the extreme ultraviolet at FLASH is measured by interfering two time-delayed partial beams directly on a CCD camera. Wavelengths between λ=32 nm and λ=8 nm are examined. A decrease of the coherence time for the fundamental wavelengths from τ_{c}=(6±0.5) fs at 32 nm to τ_{c}=(2.9±0.5) fs at 8 nm is measured. At λ=8 nm the fundamental wavelength and the third harmonic of 24 nm are compared to each other. For 8 nm radiation as third harmonic of 24 nm a coherence time of τ_{c}=(2.5±0.5) fs is observed. The spatial coherence of 24 and 8 nm fundamental pulses are found to be very similar. The visibility decreases to 50% of the maximum visibility at about 3.2 mm overlap of the partial beams, which corresponds to 42% of the beam diameter at a distance of 90 m from the exit of the undulator. These results are analyzed in terms of the Gaussian Schell model resulting in six contributing modes to the total radiation. In addition, the correlation of the visibility between the fundamental radiation at 24 nm and its third harmonic at λ=8 nm is investigated for identical shots.

The split-and-delay unit (SDU) at FLASH2 will be upgraded to enable the simultaneous operation of two temporally, spatially and spectrally separated probe beams when the free-electron laser undulators are operated in a two-color scheme. By means of suitable thin filters and an optical grating beam path a wide range of combinations of photon energies in the spectral range from 150 eV to 780 eV can be chosen. In this paper, simulations of the spectral transmission and performance parameters of the filter technique are discussed, along with a monochromator with dispersion compensation presently under construction., (open access.)

A split-and-delay unit for the extreme ultraviolet and soft X-ray spectral regions has been built which enables time-resolved experiments at beamlines FL23 and FL24 at the Free-electron LASer in Hamburg (FLASH). Geometric wavefront splitting at a sharp edge of a beam splitting mirror is applied to split the incoming soft X-ray pulse into two beams. Ni and Pt coatings at grazing incidence angles have been chosen in order to cover the whole spectral range of FLASH2 and beyond, up to hν = 1800 eV. In the variable beam path with a grazing incidence angle of ϑ d = 1.8°, the total transmission (T) ranges are of the order of 0.48 < T < 0.84 for hν < 100 eV and T > 0.50 for 100 eV < hν < 650 eV with the Ni coating, and T > 0.06 for hν < 1800 eV for the Pt coating. For a fixed beam path with a grazing incidence angle of ϑ f = 1.3°, a transmission of T > 0.61 with the Ni coating and T > 0.23 with a Pt coating is achieved. Soft X-ray pump/soft X-ray probe experiments are possible within a delay range of -5 ps < Δt < +18 ps with a nominal time resolution of t r = 66 as and a measured timing jitter of t j = 121 ± 2 as. First experiments with the split-and-delay unit determined the averaged coherence time of FLASH2 to be τ c = 1.75 fs at λ = 8 nm, measured at a purposely reduced coherence of the free-electron laser., (open access.)

We performed a time-resolved spectroscopy experiment on the dissociation of oxygen molecules after the interaction with intense extreme-ultraviolet (XUV) light from the free-electron laser in Hamburg at Deutsches Elektronen-Synchrotron. Using an XUV-pump/XUV-probe transient-absorption geometry with a split-and-delay unit, we observe the onset of electronic transitions in the O 2+ cation near 50 eV photon energy, marking the end of the progression from a molecule to two isolated atoms. We observe two different time scales of 290 ± 53 and 180 ± 76 fs for the emergence of different ionic transitions, indicating different dissociation pathways taken by the departing oxygen atoms. With regard to the emerging opportunities of tuning the central frequencies of pump and probe pulses and of increasing the probe-pulse bandwidth, future pump-probe transient-absorption experiments are expected to provide a detailed view of the coupled nuclear and electronic dynamics during molecular dissociation.

The emergence of ultra-intense extreme-ultraviolet (XUV) and X-ray free-electron lasers (FELs) has opened the door for the experimental realization of non-linear XUV and X-ray spectroscopy techniques. Here we demonstrate an experimental setup for an all-XUV transient absorption spectroscopy method for gas-phase targets at the FEL. The setup combines a high spectral resolving power of E/ΔE ≈ 1500 with sub-femtosecond interferometric resolution, and covers a broad XUV photon-energy range between approximately 20 and 110 eV. We demonstrate the feasibility of this setup firstly on a neon target. Here, we intensity- and time-resolve key aspects of non-linear XUV-FEL light-matter interactions, namely the non-resonant ionization dynamics and resonant coupling dynamics of bound states, including XUV-induced Stark shifts of energy levels. Secondly, we show that this setup is capable of tracking the XUV-initiated dissociation dynamics of small molecular targets (oxygen and diiodomethane) with site-specific resolution, by measuring the XUV transient absorption spectrum. In general, benefitting from a single-shot detection capability, we show that the setup and method provides single-shot phase-locked XUV pulse pairs. This lays the foundation to perform, in the future, experiments as a function of the XUV interferometric time delay and the relative phase, which enables advanced coherent non-linear spectroscopy schemes in the XUV and X-ray spectral range.

High-intensity ultrashort pulses at extreme ultraviolet (XUV) and x-ray photon energies, delivered by state-of-the-art free-electron lasers (FELs), are revolutionizing the field of ultrafast spectroscopy. For crossing the next frontiers of research, precise, reliable and practical photonic tools for the spectro-temporal characterization of the pulses are becoming steadily more important. Here, we experimentally demonstrate a technique for the direct measurement of the frequency chirp of extreme-ultraviolet free-electron laser pulses based on fundamental nonlinear optics. It is implemented in XUV-only pump-probe transient-absorption geometry and provides in-situ information on the time-energy structure of FEL pulses. Using a rate-equation model for the time-dependent absorbance changes of an ionized neon target, we show how the frequency chirp can be directly extracted and quantified from measured data. Since the method does not rely on an additional external field, we expect a widespread implementation at FELs benefiting multiple science fields by in-situ on-target measurement and optimization of FEL-pulse properties.

For the High-Energy-Density (HED) beamline at the SASE2 undulator of the European XFEL, a hard X-ray split-and-delay unit (SDU) has been built enabling time-resolved pump/probe experiments with photon energies between 5 keV and 24 keV. The optical layout of the SDU is based on geometrical wavefront splitting and multilayer Bragg mirrors. Maximum delays between Δτ = ±1 ps at 24 keV and Δτ = ±23 ps at 5 keV will be possible. Time-dependent wavefront propagation simulations were performed by means of the Synchrotron Radiation Workshop (SRW) software in order to investigate the impact of the optical layout, including diffraction on the beam splitter and recombiner edges and the three-dimensional topography of all eight mirrors, on the spatio-temporal properties of the XFEL pulses. The radiation is generated from noise by the code FAST which simulates the self-amplified spontaneous emission (SASE) process. A fast Fourier transformation evaluation of the disturbed interference pattern yields for ideal mirror surfaces a coherence time of τ c = 0.23 fs and deduces one of τ c = 0.21 fs for the real mirrors, thus with an error of Δτ = 0.02 fs which is smaller than the deviation resulting from shot-to-shot fluctuations of SASE2 pulses. The wavefronts are focused by means of compound refractive lenses in order to achieve fluences of a few hundred mJ mm -2 within a spot width of 20 µm (FWHM) diameter. Coherence effects and optics imperfections increase the peak intensity between 200 and 400% for pulse delays within the coherence time. Additionally, the influence of two off-set mirrors in the HED beamline are discussed. Further, we show the fluence distribution for Δz = ±3 mm around the focal spot along the optical axis. The simulations show that the topographies of the mirrors of the SDU are good enough to support X-ray pump/X-ray probe experiments., (open access.)

The free-free opacity in plasmas is fundamental to our understanding of energy transport in stellar interiors and for inertial confinement fusion research. However, theoretical predictions in the challenging dense plasma regime are conflicting and there is a dearth of accurate experimental data to allow for direct model validation. Here we present time-resolved transmission measurements in solid-density Al heated by an XUV free-electron laser. We use a novel functional optimization approach to extract the temperature-dependent absorption coefficient directly from an oversampled pool of single-shot measurements, and find a pronounced enhancement of the opacity as the plasma is heated to temperatures of order of the Fermi energy. Plasma heating and opacity enhancement are observed on ultrafast timescales, within the duration of the femtosecond XUV pulse. We attribute further rises in the opacity on ps timescales to melt and the formation of warm dense matter.

Cutaneous squamous cell carcinoma (cSCC) is the second most common form of skin cancer and is associated with cumulative UV exposure. Studies have shown that prolonged voriconazole use promotes cSCC formation; however, the biological mechanisms responsible for the increased incidence remain unclear. Here, we show that voriconazole directly increases oxidative stress in human keratinocytes and promotes UV-induced DNA damage as determined by comet assay, 8-oxoguanine immunofluorescence and mass spectrometry. Voriconazole treatment of human keratinocytes potentiates UV-induced apoptosis and activation of the p38 MAP kinase and 53BP1 UV stress response pathways. The p38 MAP kinase activation promoted by voriconazole exposure can be mitigated by pretreating keratinocytes with N-acetylcysteine. Voriconazole increases oxidative stress in keratinocytes by directly inhibiting catalase leading to lower intracellular NADPH levels and the triazole moieties in voriconazole are critical for inhibiting catalase. Furthermore, voriconazole is shown to promote UV-induced dysplasia in an in vivo model. Together, these data demonstrate that voriconazole potentiates oxidative stress in UV-irradiated keratinocytes through catalase inhibition. Use of antioxidants may mitigate the pro-oncogenic effects of voriconazole., (© 2019 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

We demonstrate time-resolved nonlinear extreme-ultraviolet absorption spectroscopy on multiply charged ions, here applied to the doubly charged neon ion, driven by a phase-locked sequence of two intense free-electron laser pulses. Absorption signatures of resonance lines due to 2p-3d bound-bound transitions between the spin-orbit multiplets ^{3}P&#95;{0,1,2} and ^{3}D&#95;{1,2,3} of the transiently produced doubly charged Ne^{2+} ion are revealed, with time-dependent spectral changes over a time-delay range of (2.4±0.3)  fs. Furthermore, we observe 10-meV-scale spectral shifts of these resonances owing to the ac Stark effect. We use a time-dependent quantum model to explain the observations by an enhanced coupling of the ionic quantum states with the partially coherent free-electron laser radiation when the phase-locked pump and probe pulses precisely overlap in time.

The photochemical processing of a CH 4  : D 2 O 1 : 3.3 ice mixture adsorbed on an HOPG surface in the XUV regime was investigated using pulses obtained from the Free-electron LASer in Hamburg (FLASH) facility. Ice films were exposed to femtosecond pulses with a photon energy of hν = 40.8 eV, consistent with the HeII resonance line. Cationic species desorbing directly from the ice films were detected using time-of-flight (ToF) mass spectrometry. Simple ions formed through the fragmentation of the parent molecules and subsequent recombination reactions were detected and are consistent with efficient D + and H + ejection from the parent species, similar to the case for low energy electron irradiation. The FEL fluence dependencies of these ions are linear or exhibit a non-linear order of up to 3. In addition, a series of C n + cluster ions (with n up to 12) were also identified. These ions display a highly non-linear desorption yield with respect to the FEL fluence, having an order of 6-10, suggesting a complex multi-step process involving the primary products of CH 4 fragmentation. Two-pulse correlation measurements were performed to gain further insight into the underlying reaction dynamics of the photo-chemical reactions. The yield of the D 2 O derived products displayed a different temporal behaviour with respect to the C n + ions, indicating the presence of very different reaction pathways to the two families of ionic products.

We present an extreme ultraviolet (EUV) microscope using a Schwarzschild objective which is optimized for single-shot sub-micrometer imaging of laser-plasma targets. The microscope has been designed and constructed for imaging the scattering from an EUV-heated solid-density hydrogen jet. Imaging of a cryogenic hydrogen target was demonstrated using single pulses of the free-electron laser in Hamburg (FLASH) free-electron laser at a wavelength of 13.5 nm. In a single exposure, we observe a hydrogen jet with ice fragments with a spatial resolution in the sub-micrometer range. In situ EUV imaging is expected to enable novel experimental capabilities for warm dense matter studies of micrometer-sized samples in laser-plasma experiments.

We studied the nanoplasma formation and explosion dynamics of single large xenon clusters in ultrashort, intense x-ray free-electron laser pulses via ion spectroscopy. The simultaneous measurement of single-shot diffraction images enabled a single-cluster analysis that is free from any averaging over the cluster size and laser intensity distributions. The measured charge state-resolved ion energy spectra show narrow distributions with peak positions that scale linearly with final ion charge state. These two distinct signatures are attributed to highly efficient recombination that eventually leads to the dominant formation of neutral atoms in the cluster. The measured mean ion energies exceed the value expected without recombination by more than an order of magnitude, indicating that the energy release resulting from electron-ion recombination constitutes a previously unnoticed nanoplasma heating process. This conclusion is supported by results from semiclassical molecular dynamics simulations.

We use a Mach-Zehnder type autocorrelator to split and delay XUV pulses from the FLASH soft X-ray laser for triggering and subsequently probing the explosion of aerosolised sugar balls. FLASH was running at 182 eV photon energy with pulses of 70 fs duration. The delay between the pump-probe pulses was varied between zero and 5 ps, and the pulses were focused to reach peak intensities above 10¹⁶W/cm² with an off-axis parabola. The direct pulse triggered the explosion of single aerosolised sucrose nano-particles, while the delayed pulse probed the exploding structure. The ejected ions were measured by ion time of flight spectrometry, and the particle sizes were measured by coherent diffractive imaging. The results show that sucrose particles of 560-1000 nm diameter retain their size for about 500 fs following the first exposure. Significant sample expansion happens between 500 fs and 1 ps. We present simulations to support these observations.

We investigate subpicosecond dynamics of warm dense hydrogen at the XUV free-electron laser facility (FLASH) at DESY (Hamburg). Ultrafast impulsive electron heating is initiated by a ≤ 300-fs short x-ray burst of 92-eV photon energy. A second pulse probes the sample via x-ray scattering at jitter-free variable time delay. We show that the initial molecular structure dissociates within (0.9 ± 0.2) ps, allowing us to infer the energy transfer rate between electrons and ions. We evaluate Saha and Thomas-Fermi ionization models in radiation hydrodynamics simulations, predicting plasma parameters that are subsequently used to calculate the static structure factor. A conductivity model for partially ionized plasma is validated by two-temperature density-functional theory coupled to molecular dynamic simulations and agrees with the experimental data. Our results provide important insights and the needed experimental data on transport properties of dense plasmas.

A tunable two-color multilayer Bragg coating capable of simultaneously reflecting the fundamental and the third harmonic of an x-ray free-electron laser at the same angle and with high reflectance R>0.70 is presented. The novel coating will enable two-color x-ray pump/x-ray probe experiments. This mirror consists of a Si substrate that is coated with two different types of multilayer systems, Mo/B4C layers with a periodicity of d=3. nm directly on the substrate and Ni/B4C layers with a periodicity of d=11.85 nm on top. Fundamental radiation with photon energies between 3 and 9 keV is reflected by a Ni/B4C multilayer system while the third harmonic (9 keV

We report on the dynamics of ultrafast heating in cryogenic hydrogen initiated by a ≲300  fs, 92 eV free electron laser x-ray burst. The rise of the x-ray scattering amplitude from a second x-ray pulse probes the transition from dense cryogenic molecular hydrogen to a nearly uncorrelated plasmalike structure, indicating an electron-ion equilibration time of ∼0.9  ps. The rise time agrees with radiation hydrodynamics simulations based on a conductivity model for partially ionized plasma that is validated by two-temperature density-functional theory.

Intermolecular reactions in and on icy films on silicate and carbonaceous grains constitute a major route for the formation of new molecular constituents in interstellar molecular clouds. In more diffuse regions and in protoplanetary discs, energetic radiation can trigger reaction routes far from thermal equilibrium. As an analog of interstellar ice-covered dust grains, highly-oriented pyrolytic graphite (HOPG) covered with D2O, NO, and H atoms is irradiated by ultrashort XUV pulses and the desorbing ionic and neutral products are analysed. The yields of several products show a nonlinear intensity dependence and thus enable the elucidation of reaction dynamics by two-pulse correlated desorption.

The temporal coherence properties of soft x-ray free electron laser pulses at FLASH are measured at 23.9 nm by interfering two time-delayed partial beams directly on a CCD camera. The partial beams are obtained by wave front beam splitting in an autocorrelator operating at photon energies from h nu = 30 to 200 eV. At zero delay a visibility of (0.63+/- 0.04) is measured. The delay of one partial beam reveals a coherence time of 6 fs at 23.9 nm. The visibility further displays a non-monotonic decay, which can be rationalized by the presence of multiple pulse structure.