Free-electron lasers (FELs) enable the study of the ultrafast dynamics of photocatalytic reactions by time-resolved X-ray photoelectron spectroscopy (tr-XPS) with femtosecond time resolution. In an optical pump - soft X-ray probe photoemission experiment conducted at the free-electron laser in Hamburg (FLASH), we observed the ultrafast oxidation of CO to CO2 on rutile TiO2(110) by monitoring the O 1s core level region. Within 800± 250 fs after laser excitation, CO2 as a product of the photooxidation of CO is detected. Based on density functional theory calculations, we propose that the oxygen activation pathway for the CO oxidation is initiated via an O2-TiO2 charge transfer complex directly excited by the 770 nm pump laser. Our results give insight into the fundemental understanding of photocatalytic processes of TiO2 polymorphs relevant for the design of more efficient photoctalaysts.

Ultrashort XUV pulses of the Free-Electron-LASer in Hamburg (FLASH) were used to investigate laser-induced fragmentation patterns of the prototypical chiral molecule 1-iodo-2-methyl-butane (C_5H_11I) in a pump-probe scheme. Ion velocity-map images and mass spectra of optical-laser-induced fragmentation were obtained for subsequent FEL exposure with photon energies of 63 eV and 75 eV. These energies specifically address the iodine 4d edge of neutral and singly charged iodine, respectively. The presented ion spectra for two optical pump-laser wavelengths, i.e., 800 nm and 267 nm, reveal substantially different cationic fragment yields in dependence on the wavelength and intensity. For the case of 800-nm-initiated fragmentation, the molecule dissociates notably slower than for the 267-nm pump. The results underscore the importance of considering optical-laser wavelength and intensity in the dissociation dynamics of this prototypical chiral molecule that is a promising candidate for future studies of its asymmetric nature.

Percival is a CMOS-based imager with 2 megapixels, also called P2M, designed for photon science experiments. The first generation of the P2M sensor showed some performance issues. Specifically, ADCs in full-speed operation mode are affected by crosstalk and show a non-linear and uncorrectable response. A firmware hack to the readout and data acquisition system has been introduced to partially overcome these effects, at the cost of limiting the frame rate to 83 Hz. Moreover, a non-uniform dark response of the sensor pixels is observed, explained by non-uniform bias currents across the chip: two opposite edges of the sensor cannot be digitized when applying biases that have the centre of the sensor operating normally. These issues are addressed in the re-submission of the chip. In this contribution, we present the current status of the detector and the first results from the re-designed sensor.

Time-resolved absorption spectroscopy and magnetic circular dichroism with circularly polarized soft x-rays (XAS and XMCD) are powerful tools to probe electronic and magnetic dynamics in magnetic materials element- and site-selectively. By employing these methods, groundbreaking results have been obtained, for instance, for magnetic alloys, which helped to fundamentally advance the field of ultrafast magnetization dynamics. At the free-electron laser facility FLASH, key capabilities for ultrafast XAS and XMCD experiments have recently improved. In an upgrade, an APPLE-III helical afterburner undulator was installed at FLASH2 in September 2023. This installation allows for the generation of circularly polarized soft x-ray pulses with a duration of a few tens of femtoseconds covering the L 3 , 2 -edges of the important 3d transition metal elements with pulse energies of several μ J. Here, we present first experimental results with such ultrashort x-ray pulses from the FL23 beamline employing XMCD at the L 3 , 2 -edges of the 3d metals, Co, Fe, and Ni. We obtain significant dichroic difference signals indicating a degree of circular polarization close to 100%. With the pulse-length preserving monochromator at beamline FL23 and an improved pump-laser setup, FLASH can offer important and efficient experimental instrumentation for ultrafast demagnetization studies and other investigations of ultrafast spin dynamics in 3d transition metals, multilayers, and alloys.

Pump-probe methods are a ubiquitous tool in the field of ultrafast dynamic measurements. In recent years, x-ray free-electron laser experiments have gained importance due to their ability to probe with high chemical selectivity and at atomic length scales. Measurements are typically repeated many thousands of times to collect sufficient statistics and vary parameters like delay or fluence, necessitating that initial conditions are restored each time. An alternative is presented by experiments which measure the relevant parameters in a single shot. Here, we present a time-to-space mapping imaging scheme that enables us to record a range of delays and laser fluences in any single shot of the x-ray probe. We demonstrate the use of this scheme by mapping the ultrafast dynamics of the optically induced insulator-to-metal Verwey transition in a magnetite thin film, probed by soft x-ray resonant diffraction. By extrapolating our results toward the conditions found at x-ray free-electron lasers with higher photon energy, we demonstrate that the presented data could be recorded in a single shot.

The use of advanced x-ray sources plays a key role in the study of dynamic processes in magnetically ordered materials. The progress in x-ray free-electron lasers enables the direct and simultaneous observation of the femtosecond evolution of electron and spin systems through transient x-ray absorption spectroscopy and x-ray magnetic circular dichroism, respectively. Such experiments allow us to resolve the response seen in the population of the spin-split valence states upon optical excitation. Here, we utilize circularly polarized ultrashort soft x-ray pulses from the new helical afterburner undulator at the free-electron laser FLASH in Hamburg to study the femtosecond dynamics of a laser-excited CoPt alloy at the Co L3-edge absorption. Despite employing a weaker electronic excitation level, we find a comparable demagnetization for the Co 3d-states in CoPt compared to previous measurements on CoPd. This is attributed to the distinctly different spin–orbit coupling between 3d and 4d vs 3d and 5d elements in the corresponding alloys and multilayers.

A change of orbital state alters the coupling between ions and their surroundings drastically. Orbital excitations are hence key to understand and control interaction of ions. Rare-earth elements with strong magneto-crystalline anisotropy (MCA) are important ingredients for magnetic devices. Thus, control of their localized 4 f magnetic moments and anisotropy is one major challenge in ultrafast spin physics. With time-resolved x-ray absorption and resonant inelastic scattering experiments, we show for Tb metal that 4 f -electronic excitations out of the ground-state multiplet occur after optical pumping. These excitations are driven by inelastic 5 d -4 f -electron scattering, altering the 4 f -orbital state and consequently the MCA with important implications for magnetization dynamics in 4 f -metals and more general for the excitation of localized electronic states in correlated materials.

Photoemission from a solid surface provides a wealth of information about the electronic structure of the surface and its dynamic evolution. Ultrafast pump-probe experiments are particularly useful to study the dynamic interactions of photons with surfaces as well as the ensuing electron dynamics induced by these interactions. Time-resolved laser-assisted photoemission (tr-LAPE) from surfaces is a novel technique to gain deeper understanding of the fundamentals underlying the photoemission process. Here, we present the results of a femtosecond time-resolved soft X-ray photoelectron spectroscopy experiment on two different metal surfaces conducted at the X-ray Free-Electron Laser FLASH in Hamburg. We study photoemission from the W 4f and Pt 4f core levels using ultrashort soft X-ray pulses in combination with synchronized infrared (IR) laser pulses. When both pulses overlap in time and space, laser-assisted photoemission results in the formation of a series of sidebands that reflect the dynamics of the laser-surface interaction. We demonstrate a qualitatively new level of sideband generation up to the sixth order and a surprising material dependence of the number of sidebands that has so far not been predicted by theory. We provide a semi-quantitative explanation of this phenomenon based on the different dynamic dielectric responses of the two materials. Our results advance the understanding of the LAPE process and reveal new details of the IR field present in the surface region, which is determined by the dynamic interplay between the IR laser field and the dielectric response of the metal surfaces.

Abstract Charge-transfer excitations are of paramount importance for understanding the electronic structure of copper-oxide based high-temperature superconductors. In this study, we investigate the response of a Bi $$_2$$ 2 Sr $$_2$$ 2 CaCu $$_2$$ 2 O $$_{\textrm{8}+ \delta }$$ 8 + δ crystal to the charge redistribution induced by an infrared ultrashort pulse. Element-selective time-resolved core-level photoelectron spectroscopy with a high energy resolution allows disentangling the dynamics of oxygen ions with different coordination and bonds thanks to their different chemical shifts. Our experiment shows that the O 1s component arising from the Cu–O planes is significantly perturbed by the infrared light pulse. Conversely, the apical oxygen, also coordinated with Sr ions in the Sr-O planes, remains unaffected. This result highlights the peculiar behavior of the electronic structure of the Cu–O planes. It also unlocks the way to study the out-of-equilibrium electronic structure of copper-oxide-based high-temperature superconductors by identifying the O 1s core-level emission originating from the oxygen ions in the Cu–O planes. This ability could be critical to gain information about the strongly-correlated electron ultrafast dynamical mechanisms in the Cu–O plane in the normal and superconducting phases.

Femtosecond light-induced phase transitions between different macroscopic orders provide the possibility to tune the functional properties of condensed matter on ultrafast timescales. In first-order phase transitions, transient non-equilibrium phases and inherent phase coexistence often preclude non-ambiguous detection of transition precursors and their temporal onset. Here, we present a study combining time-resolved photoelectron spectroscopy and ab-initio electron dynamics calculations elucidating the transient subpicosecond processes governing the photoinduced generation of ferromagnetic order in antiferromagnetic FeRh. The transient photoemission spectra are accounted for by assuming that not only the occupation of electronic states is modified during the photoexcitation process. Instead, the photo-generated non-thermal distribution of electrons modifies the electronic band structure. The ferromagnetic phase of FeRh, characterized by a minority band near the Fermi energy, is established 350 ± 30 fs after the laser excitation. Ab-initio calculations indicate that the phase transition is initiated by a photoinduced Rh-to-Fe charge transfer.

Recent developments in X-ray free-electron lasers have enabled a novel site-selective probe of coupled nuclear and electronic dynamics in photoexcited molecules, time-resolved X-ray photoelectron spectroscopy (TRXPS). We present results from a joint experimental and theoretical TRXPS study of the well-characterized ultraviolet photodissociation of CS2, a prototypical system for understanding non-adiabatic dynamics. These results demonstrate that the sulfur 2p binding energy is sensitive to changes in the nuclear structure following photoexcitation, which ultimately leads to dissociation into CS and S photoproducts. We are able to assign the main X-ray spectroscopic features to the CS and S products via comparison to a first-principles determination of the TRXPS based on ab initio multiple-spawning simulations. Our results demonstrate the use of TRXPS as a local probe of complex ultrafast photodissociation dynamics involving multimodal vibrational coupling, nonradiative transitions between electronic states, and multiple final product channels.

We present an approach that combines photon spectrum correlation analysis with the reconstruction of three-dimensional momentum distribution from velocity map images in an efficient, single-step procedure. We demonstrate its efficacy with the results from the photoionization of the 2 p-shell of argon using the Free-electron LASer in Hamburg free-electron laser (FEL). Distinct spectral features due to the spin-orbit splitting of Ar+(2p(-1)) are resolved, despite the large average bandwidth of the ionizing pulses from the FEL. This demonstrates a clear advantage over the conventional analysis method, and it will be broadly beneficial for velocity map imaging experiments with FEL sources. The retrieved linewidth of the binding energy spectrum approaches the resolution limitation prescribed by the spectrometers used to collect the data. Our approach presents a path to extend spectral-domain ghost imaging to the case where the photoproduct observable is high-dimensional.

Time-resolved momentum microscopy provides insight into the ultrafast interplay between structural and electronic dynamics. Here we extend orbital tomography into the time domain in combination with time-resolved momentum microscopy at a free-electron laser (FEL) to follow transient photoelectron momentum maps of excited states of a bilayer pentacene film on Ag(110). We use optical pump and FEL probe pulses by keeping FEL source conditions to minimize space charge effects and radiation damage. From the momentum microscopy signal, we obtain time-dependent momentum maps of the excited-state dynamics of both pentacene layers separately. In a combined experimental and theoretical study, we interpret the observed signal for the bottom layer as resulting from the charge redistribution between the molecule and the substrate induced by excitation. We identify that the dynamics of the top pentacene layer resembles excited-state molecular dynamics.

We have conceived and built the HILITE (High-Intensity Laser-Ion Trap Experiment) Penning-trap setup for the production, confinement and preparation of pure ensembles of highly charged ions in a defined quantum state as a target for various high-intensity lasers. This enables a broad suite of laser-ion interaction studies at high photon energies and/or intensities, such as non-linear photo-ionisation studies. The setup has now been used to perform experiments at one such laser facility, namely the FLASH Free-Electron Laser at DESY in Hamburg, Germany. We describe the experimental possibilities of the apparatus, the results of the first measurements and future experiments at other laser facilities.

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The extension of nonlinear spectroscopic techniques into the x-ray domain is in its infancy but holds the promise to provide unique insight into the dynamics of charges in photoexcited processes, which are of fundamental as well as applied interest. We report on the observation of a third order nonlinear process in lithium fluoride at a free-electron laser. Exploring the yield of four wave mixing (FWM) in resonance with transitions to strongly localized core exciton states vs. delocalized Bloch states, we find resonant FWM to be a sensitive probe for the degree of charge localization: substantial sum- and difference-frequency generation is observed exclusively when in a one- or three-photon resonance with a LiF core exciton, with a dipole forbidden transition affecting details of the nonlinear response. Our reflection-geometry-based approach to detect FWM signals enables the study of a wide variety of condensed matter sample systems, provides atomic selectivity via resonant transitions and can be easily scaled to shorter wavelengths at free electron x-ray lasers.

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 4d 3/2 and 4d 5/2 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.

Wide-band-gap insulators such as NiO offer the exciting prospect of coherently manipulating electronic correlations with strong optical fields. Contrary to metals where rapid dephasing of optical excitation via electronic processes occurs, the sub-gap excitation in charge-transfer insulators has been shown to couple to low-energy bosonic excitations. However, it is currently unknown if the bosonic dressing field is composed of phonons or magnons. Here we use the prototypical charge-transfer insulator NiO to demonstrate that 1.5 eV sub-gap optical excitation leads to a renormalised NiO band-gap in combination with a significant reduction of the antiferromagnetic order. We employ element-specific X-ray reflectivity at the FLASH free-electron laser to demonstrate the reduction of the upper band-edge at the O 1s-2p core-valence resonance (K-edge) whereas the antiferromagnetic order is probed via X-ray magnetic linear dichroism (XMLD) at the Ni 2p-3d resonance (L2-edge). Comparing the transient XMLD spectral line shape to ground-state measurements allows us to extract a spin temperature rise of 65 +/- 5 K for time delays longer than 400 fs while at earlier times a non-equilibrium spin state is formed. We identify transient mid-gap states being formed during the first 200 fs accompanied by a band-gap reduction lasting at least up to the maximum measured time delay of 2.4 ps. Electronic structure calculations indicate that magnon excitations significantly contribute to the reduction of the NiO band gap.

In this work, we use an extreme-ultraviolet (XUV) free-electron laser (FEL) to resonantly excite the I:4d(5/2)(-sigma*) transition of a gas-phase di-iodomethane (CH2I2) target. This site-specific excitation generates a 4d core hole located at an iodine site, which leaves the molecule in a well-defined excited state. We subsequently measure the time-dependent absorption change of the molecule with the FEL probe spectrum centered on the same I: 4d resonance. Using ab initio calculations of absorption spectra of a transient isomerization pathway observed in earlier studies, our time-resolved measurements allow us to assign the timescales of the previously reported direct and indirect dissociation pathways. The presented method is thus sensitive to excited-state molecular geometries in a time-resolved manner, following a core-resonant site-specific trigger.