The soft X-ray and XUV split-and-delay unit at beamlines FL23/24 at FLASH2.

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 ϑd = 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 ϑf = 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 tr = 66 as and a measured timing jitter of tj = 121 ± 2 as. First experiments with the split-and-delay unit determined the averaged coherence time of FLASH2 to be τc = 1.75 fs at λ = 8 nm, measured at a purposely reduced coherence of the free-electron laser.

Differential Measurement of Electron Ejection after Two-Photon Two-Electron Excitation of Helium.

We report the measurement of the photoelectron angular distribution of two-photon single-ionization near the 2p^{2} ^{1}D^{e} double-excitation resonance in helium, benchmarking the fundamental nonlinear interaction of two photons with two correlated electrons. This observation is enabled by the unique combination of intense extreme ultraviolet pulses, delivered at the high-repetition-rate free-electron laser in Hamburg (FLASH), ionizing a jet of cryogenically cooled helium atoms in a reaction microscope. The spectral structure of the intense self-amplified spontaneous emission free-electron laser pulses has been resolved on a single-shot level to allow for post selection of pulses, leading to an enhanced spectral resolution, and introducing a new experimental method. The measured angular distribution is directly compared to state-of-the-art theory based on multichannel quantum defect theory and the streamlined R-matrix method. These results and experimental methodology open a promising route for exploring fundamental interactions of few photons with few electrons in general.

XUV pump-XUV probe transient absorption spectroscopy at FELs.

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.

XUV-Initiated Dissociation Dynamics of Molecular Oxygen (O2).

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 O2+ 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.

Reaction microscope endstation at FLASH2.

A reaction microscope dedicated to multi-particle coincidence spectroscopy on gas-phase samples is installed at beamline FL26 of the free-electron laser FLASH2 in Hamburg. The main goals of the instrument are to follow the dynamics of atoms, molecules and small clusters on their natural time-scale and to study non-linear light-matter interaction with such systems. To this end, the reaction microscope is combined with an in-line extreme-ultraviolet (XUV) split-delay and focusing optics, which allows time-resolved XUV-XUV pump-probe spectroscopy to be performed.

Terahertz-Field-Induced Time Shifts in Atomic Photoemission.

Time delays for atomic photoemission obtained in streaking or reconstruction of attosecond bursts by interference of two-photon transitions experiments originate from a combination of the quantum mechanical Wigner time and the Coulomb-laser coupling. While the former was investigated intensively theoretically as well as experimentally, the latter attracted less interest in experiments and has mostly been subject to calculations. Here, we present a measurement of the Coulomb-laser coupling-induced time shifts in photoionization of neon at 59.4 eV using a terahertz (THz) streaking field (λ=152 µm). Employing a reaction microscope at the THz beamline of the free-electron laser in Hamburg (FLASH), we have measured relative time shifts of up to 70 fs between the emission of 2p photoelectrons (∼38 eV) and low-energetic (<1 eV) photoelectrons. A comparison with theoretical predictions on Coulomb-laser coupling reveals reasonably good agreement.

Strong-Field Extreme-Ultraviolet Dressing of Atomic Double Excitation.

We report on the experimental observation of a strong-field dressing of an autoionizing two-electron state in helium with intense extreme-ultraviolet laser pulses from a free-electron laser. The asymmetric Fano line shape of this transition is spectrally resolved, and we observe modifications of the resonance asymmetry structure for increasing free-electron-laser pulse energy on the order of few tens of Microjoules. A quantum-mechanical calculation of the time-dependent dipole response of this autoionizing state, driven by classical extreme-ultraviolet (XUV) electric fields, evidences strong-field-induced energy and phase shifts of the doubly excited state, which are extracted from the Fano line-shape asymmetry. The experimental results obtained at the Free-Electron Laser in Hamburg (FLASH) thus correspond to transient energy shifts on the order of a few meV, induced by strong XUV fields. These results open up a new way of performing nonperturbative XUV nonlinear optics for the light-matter interaction of resonant electronic transitions in atoms at short wavelengths.

Nonlinear Coherence Effects in Transient-Absorption Ion Spectroscopy with Stochastic Extreme-Ultraviolet Free-Electron Laser Pulses.

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_{0,1,2} and ^{3}D_{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.

Tracing charge transfer in argon dimers by XUV-pump IR-probe experiments at FLASH.

Charge transfer (CT) at avoided crossings of excited ionized states of argon dimers is observed using a two-color pump-probe experiment at the free-electron laser in Hamburg (FLASH). The process is initiated by the absorption of three 27-eV-photons from the pump pulse, which leads to the population of Ar2+*-Ar states. Due to nonadiabatic coupling between these one-site doubly ionized states and two-site doubly ionized states of the type Ar+*-Ar+, CT can take place leading to the population of the latter states. The onset of this process is probed by a delayed infrared (800 nm) laser pulse. The latter ionizes the dimers populating repulsive Ar2+ -Ar+ states, which then undergo a Coulomb explosion. From the delay-dependent yields of the obtained Ar2+ and Ar+ ions, the lifetime of the charge-transfer process is extracted. The obtained experimental value of (531 ± 136) fs agrees well with the theoretical value computed from Landau-Zener probabilities.

XUV double-pulses with femtosecond to 650†ps separation from a multilayer-mirror-based split-and-delay unit at FLASH.

Extreme ultraviolet (XUV) and X-ray free-electron lasers enable new scientific opportunities. Their ultra-intense coherent femtosecond pulses give unprecedented access to the structure of undepositable nanoscale objects and to transient states of highly excited matter. In order to probe the ultrafast complex light-induced dynamics on the relevant time scales, the multi-purpose end-station CAMP at the free-electron laser FLASH has been complemented by the novel multilayer-mirror-based split-and-delay unit DESC (DElay Stage for CAMP) for time-resolved experiments. XUV double-pulses with delays adjustable from zero femtoseconds up to 650 picoseconds are generated by reflecting under near-normal incidence, exceeding the time range accessible with existing XUV split-and-delay units. Procedures to establish temporal and spatial overlap of the two pulses in CAMP are presented, with emphasis on the optimization of the spatial overlap at long time-delays via time-dependent features, for example in ion spectra of atomic clusters.

CAMP@FLASH: an end-station for imaging, electron- and ion-spectroscopy, and pump-probe experiments at the FLASH free-electron laser.

The non-monochromatic beamline BL1 at the FLASH free-electron laser facility at DESY was upgraded with new transport and focusing optics, and a new permanent end-station, CAMP, was installed. This multi-purpose instrument is optimized for electron- and ion-spectroscopy, imaging and pump-probe experiments at free-electron lasers. It can be equipped with various electron- and ion-spectrometers, along with large-area single-photon-counting pnCCD X-ray detectors, thus enabling a wide range of experiments from atomic, molecular, and cluster physics to material and energy science, chemistry and biology. Here, an overview of the layout, the beam transport and focusing capabilities, and the experimental possibilities of this new end-station are presented, as well as results from its commissioning.

Alignment, orientation, and Coulomb explosion of difluoroiodobenzene studied with the pixel imaging mass spectrometry (PImMS) camera.

Laser-induced adiabatic alignment and mixed-field orientation of 2,6-difluoroiodobenzene (C6H3F2I) molecules are probed by Coulomb explosion imaging following either near-infrared strong-field ionization or extreme-ultraviolet multi-photon inner-shell ionization using free-electron laser pulses. The resulting photoelectrons and fragment ions are captured by a double-sided velocity map imaging spectrometer and projected onto two position-sensitive detectors. The ion side of the spectrometer is equipped with a pixel imaging mass spectrometry camera, a time-stamping pixelated detector that can record the hit positions and arrival times of up to four ions per pixel per acquisition cycle. Thus, the time-of-flight trace and ion momentum distributions for all fragments can be recorded simultaneously. We show that we can obtain a high degree of one-and three-dimensional alignment and mixed-field orientation and compare the Coulomb explosion process induced at both wavelengths.

Recombination-Enhanced Surface Expansion of Clusters in Intense Soft X-Ray Laser Pulses.

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.

Explosion dynamics of sucrose nanospheres monitored by time of flight spectrometry and coherent diffractive imaging at the split-and-delay beam line of the FLASH soft X-ray laser.

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.

Generation and structure of extremely large clusters in pulsed jets.

Extremely large xenon clusters with sizes exceeding the predictions of the Hagena scaling law by several orders of magnitude are shown to be produced in pulsed gas jets. The cluster sizes are determined using single-shot single-particle imaging experiments with short-wavelength light pulses from the free-electron laser in Hamburg (FLASH). Scanning the time delay between the pulsed cluster source and the intense femtosecond x-ray pulses first shows a main plateau with size distributions in line with the scaling laws, which is followed by an after-pulse of giant clusters. For the extremely large clusters with radii of several hundred nanometers the x-ray scattering patterns indicate a grainy substructure of the particles, suggesting that they grow by cluster coagulation.

Femtosecond time-delay X-ray holography.

Extremely intense and ultrafast X-ray pulses from free-electron lasers offer unique opportunities to study fundamental aspects of complex transient phenomena in materials. Ultrafast time-resolved methods usually require highly synchronized pulses to initiate a transition and then probe it after a precisely defined time delay. In the X-ray regime, these methods are challenging because they require complex optical systems and diagnostics. Here we propose and apply a simple holographic measurement scheme, inspired by Newton's 'dusty mirror' experiment, to monitor the X-ray-induced explosion of microscopic objects. The sample is placed near an X-ray mirror; after the pulse traverses the sample, triggering the reaction, it is reflected back onto the sample by the mirror to probe this reaction. The delay is encoded in the resulting diffraction pattern to an accuracy of one femtosecond, and the structural change is holographically recorded with high resolution. We apply the technique to monitor the dynamics of polystyrene spheres in intense free-electron-laser pulses, and observe an explosion occurring well after the initial pulse. Our results support the notion that X-ray flash imaging can be used to achieve high resolution, beyond radiation damage limits for biological samples. With upcoming ultrafast X-ray sources we will be able to explore the three-dimensional dynamics of materials at the timescale of atomic motion.

Direct tracking of ultrafast proton transfer in water dimers.

Upon ionization, water forms a highly acidic radical cation H2O+· that undergoes ultrafast proton transfer (PT)-a pivotal step in water radiation chemistry, initiating the production of reactive H3O+, OH[Formula: see text] radicals, and a (hydrated) electron. Until recently, the time scales, mechanisms, and state-dependent reactivity of ultrafast PT could not be directly traced. Here, we investigate PT in water dimers using time-resolved ion coincidence spectroscopy applying a free-electron laser. An extreme ultraviolet (XUV) pump photon initiates PT, and only dimers that have undergone PT at the instance of the ionizing XUV probe photon result in distinct H3O+ + OH+ pairs. By tracking the delay-dependent yield and kinetic energy release of these ion pairs, we measure a PT time of (55 ± 20) femtoseconds and image the geometrical rearrangement of the dimer cations during and after PT. Our direct measurement shows good agreement with nonadiabatic dynamics simulations for the initial PT and allows us to benchmark nonadiabatic theory.

Three-dimensional femtosecond snapshots of isolated faceted nanostructures.

The structure and dynamics of isolated nanosamples in free flight can be directly visualized via single-shot coherent diffractive imaging using the intense and short pulses of x-ray free-electron lasers. Wide-angle scattering images encode three-dimensional (3D) morphological information of the samples, but its retrieval remains a challenge. Up to now, effective 3D morphology reconstructions from single shots were only achieved via fitting with highly constrained models, requiring a priori knowledge about possible geometries. Here, we present a much more generic imaging approach. Relying on a model that allows for any sample morphology described by a convex polyhedron, we reconstruct wide-angle diffraction patterns from individual silver nanoparticles. In addition to known structural motives with high symmetries, we retrieve imperfect shapes and agglomerates that were not previously accessible. Our results open unexplored routes toward true 3D structure determination of single nanoparticles and, ultimately, 3D movies of ultrafast nanoscale dynamics.

Time-resolving state-specific molecular dissociation with XUV broadband absorption spectroscopy.

The electronic and nuclear dynamics inside molecules are essential for chemical reactions, where different pathways typically unfold on ultrafast timescales. Extreme ultraviolet (XUV) light pulses generated by free-electron lasers (FELs) allow atomic-site and electronic-state selectivity, triggering specific molecular dynamics while providing femtosecond resolution. Yet, time-resolved experiments are either blind to neutral fragments or limited by the spectral bandwidth of FEL pulses. Here, we combine a broadband XUV probe pulse from high-order harmonic generation with an FEL pump pulse to observe dissociation pathways leading to fragments in different quantum states. We temporally resolve the dissociation of a specific O2+ state into two competing channels by measuring the resonances of ionic and neutral fragments. This scheme can be applied to investigate convoluted dynamics in larger molecules relevant to diverse science fields.

Measuring the frequency chirp of extreme-ultraviolet free-electron laser pulses by transient absorption spectroscopy.

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.