Transition-metal complexes are central for catalysis, material sciences and biochemistry, owing to their diverse non-radiative decay pathways driven by femtosecond-scale metal-ligand charge transfer. Resonant double-core-hole (DCH) ion-yield spectroscopy enables direct observation of ultrafast electronic and nuclear dynamics of such complexes with a direct coupling between strongly localized, transient charges and the chemically active valence electrons. Yet, previous DCH investigations were confined to atoms and small molecules at the K -edge. Here, we extend resonant DCH ion-yield spectroscopy to the L -edge of the transition-metal carbonyl Fe(CO) 5 in the gas phase to investigate fragmentation dynamics and sequential DCH ionization of the Fe center. Using intense femtosecond X-ray pulses, we observe signatures of multiply charged Fe cations, up to Fe 15+ . Comparison with atomic-level ionization-pathway modeling indicates a photon-energy range between 740eV and 780eV in which cations originating from core-excited DCH states dominate. Competing DCH channels, (i) resonant excitation following ionization or (ii) resonant-resonant excitation, govern the ionization and subsequent relaxation cascade. These channels enable charge build-up far beyond the single-core-hole (SCH) limit and induce fluence-dependent depletion of lower-charge fragments. Our results establish L -edge DCH resonance spectroscopy as a powerful approach for probing ultrafast charge redistribution and fragmentation in transition-metal complexes.

Vibrational modes of glucose spanning from 900 to 1400 cm −1 in the molecular fingerprint region have been traced by means of vibrational sum-frequency generation spectroscopy in aqueous solution as a function of glucose concentration. The high sensitivity is enabled by a 200 kHz few-cycle mid-infrared optical parametric chirped-pulse amplifier (OPCPA). The OPCPA generates broadband pulses (from 7 to 11 μ m) centered at 9 μ m with 114 fs pulse duration, at a high average power of 245 mW and high pulse energy of 1.2 μ J. The achieved performance of the spectrometer is benchmarked by probing the carbon-oxygen bond stretching mode at 1035 cm −1 using a biologically relevant low sample concentration of 10 mM.

Resonant Inelastic X-ray Scattering (RIXS) is an ideal X-ray spectroscopy method to push the combination of energy and time resolutions to the Fourier transform ultimate limit, because it is unaffected by the core-hole lifetime energy broadening. And in pump-probe experiments the interaction time is made very short by the same core-hole lifetime. RIXS is very photon hungry so it takes great advantage from high repetition rate pulsed X-ray sources like the European XFEL. The hRIXS instrument is designed for RIXS experiments in the soft X-ray range with energy resolution approaching the Fourier and the Heisenberg limits. It is based on a spherical grating with variable line spacing (VLS) and a position-sensitive 2D detector. Initially, two gratings are installed to adequately cover the whole photon energy range. With optimized spot size on the sample and small pixel detector the energy resolution can be better than 40 meV at any photon energy below 1000 eV. At the SCS instrument of the European XFEL the spectrometer can be easily positioned thanks to air-pads on a high-quality floor, allowing the scattering angle to be continuously adjusted over the 65-145 deg range. It can be coupled to two different sample interaction chamber, one for liquid jets and one for solids, each equipped at the state-of-the-art and compatible for optical laser pumping in collinear geometry. The measured performances, in terms of energy resolution and count rate on the detector, closely match design expectations. hRIXS is open to public users since the summer of 2022.

Strong electronic correlation can lead to insulating behavior and to the opening of large optical gaps, even in materials with partly filled valence shells. Although the non-equilibrium optical response encodes both local (quasi atomic) and collective (long range) responses, optical spectroscopy is usually more sensitive to the latter. Resonant x-ray techniques are better suited to investigate the quasi-atomic properties of correlated solids. Using time-resolved resonant inelastic x-ray scattering (RIXS), here we study the ultrafast non-equilibrium processes in NiO following photo-excitation by ultraviolet photons with energy exceeding the optical gap. We observe the creation of charge-transfer excitons that decay with a time constant of about 2 ps, while itinerant photo-doping persists for tens of picoseconds. Following our discovery, which establishes time-resolved high-resolution RIXS as a powerful tool for the study of transient phenomena in condensed matter, the possible presence of charge-transfer excitons will need to be considered when interpreting optical pump-probe experiments on correlated quantum materials.

The thermoelectric properties of fully sprayed thin films of poly(3-hexylthiophen-2,5-diyl) (P3HT) doped with chloroauric acid are investigated for different film thicknesses. The film thickness increases logarithmically with increasing amount of deposited material on the surfaces. Both the electrical conductivity and measured Seebeck coefficients of the doped thin films show an optimal polymer layer thickness between 275 and 310 nm and yield a maximum power factor of (1.77 ± 0.22) μW/m·K^2 . The optimum layer thickness results from the optimal amount of dopant molecules per monomer between 1.1 and 1.3 at these ratios of P3HT and HAuCl _4 for the thin film fabrication.

Tailored light-matter interactions in the strong coupling regime enable the manipulation and control of quantum systems with up to unit efficiency, with applications ranging from quantum information to photochemistry. While strong light-matter interactions are readily induced at the valence electron level using long-wavelength radiation, comparable phenomena have been only recently observed with short wavelengths, accessing highly-excited multi-electron and inner-shell electron states. However, the quantum control of strong-field processes at short wavelengths has not been possible, so far, due to the lack of pulse shaping technologies in the extreme ultraviolet (XUV) and X-ray domain. Here, exploiting pulse shaping of the seeded free-electron laser (FEL) FERMI, we demonstrate the strong-field quantum control of ultrafast Rabi dynamics in helium atoms with high fidelity. Our approach unravels a strong dressing of the ionization continuum, otherwise elusive to experimental observables. The latter is exploited to achieve control of the total ionization rate, with prospective applications in many XUV and soft X-ray experiments. Leveraging recent advances in intense few-femtosecond to attosecond XUV to soft X-ray light sources, our results open an avenue to the efficient manipulation and selective control of core electron processes and electron correlation phenomena in real time.

The coupling of electronic and nuclear motion in polyatomic molecules is at the heart of attochemistry. The molecular properties, transient structures, and reaction mechanism of these many-body quantum objects are defined on the level of electrons and ions by molecular wave functions and their coherent superposition, respectively. In the present contribution, we monitor nonadiabatic quantum wave packet dynamics during molecular charge motion by reconstructing both the oscillatory charge density distribution and the characteristic time-dependent nuclear configuration coordinate from time-resolved Auger electron spectroscopic data recorded in previous studies on glycine molecules [Schwickert et al. Sci. Adv. 2022, 8, eabn6848]. The electronic and nuclear motion on the femtosecond time scale was induced and probed in kinematically complete soft X-ray experiments at the FLASH free-electron laser facility. The detailed analysis of amplitude, instantaneous phase, and instantaneous frequency of the propagating many-body wave packet during its lifecycle provides unprecedented insight into dynamical processes beyond the Born-Oppenheimer approximation. We are confident that the refined experimental data evaluation helps to develop new theoretical tools to describe time-dependent molecular wave functions in complicated but ubiquitous non-Born-Oppenheimer photochemical conditions.

The relaxation dynamics of electronically excited 3He and 4He clusters and droplets is investigated using time-correlated near-infrared and visible (NIR/VIS) fluorescence excitation spectroscopy. A rich data set spanning a wide range of cluster and droplet sizes is produced. The spectral features broadly follow the vacuum ultraviolet excitation (VUV) spectra. However, when the NIR/VIS spectra are normalised to the VUV fluorescence, regions with distinctly different cluster size and isotope dependence are identified, enabling deeper insight into the relaxation mechanism. Particle density, location of atomic-like states and their principal quantum number, n, are found to play an important role in the relaxation. For states with n = 3 and higher, only energy within the surface region is transferred to excited atoms which are subsequently ejected from the surface and fluoresce in vacuum. For states with n = 2, energy from the entire region within clusters and droplets is transferred to the surface, leading to the ejection of excited atoms and excimers. Here, the energy is transferred by excitation hopping, which competes with radiative and non-radiative decay, making ejection and NIR/VIS fluorescence inefficient in increasingly larger droplets.

Free-electron lasers provide bright, ultrashort, and monochromatic x-ray pulses, enabling novel spectroscopic measurements not only with femtosecond temporal resolution: The high fluence of their x-ray pulses can also easily enter the regime of the non-linear x-ray–matter interaction. Entering this regime necessitates a rigorous analysis and reliable prediction of the relevant non-linear processes for future experiment designs. Here, we show non-linear changes in the L3-edge absorption of metallic nickel thin films, measured with fluences up to 60 J/cm2. We present a simple but predictive rate model that quantitatively describes spectral changes based on the evolution of electronic populations within the pulse duration. Despite its simplicity, the model reaches good agreement with experimental results over more than three orders of magnitude in fluence, while providing a straightforward understanding of the interplay of physical processes driving the non-linear changes. Our findings provide important insights for the design and evaluation of future high-fluence free-electron laser experiments and contribute to the understanding of non-linear electron dynamics in x-ray absorption processes in solids at the femtosecond timescale.

XUV fluorescence spectroscopy provides information on energy absorption and dissipation processes taking place in the interaction of helium clusters with intense femtosecond laser pulses. The present experimental results complement the physical picture derived from previous electron and ion spectroscopic studies of the generated helium nanoplasma. Here, the broadband XUV fluorescence emission from high-lying Rydberg states that covers the spectral region from 6p → 1s at 53.0 eV all the way to photon energies corresponding to the ionization potential of He^+ ions at 54.4 eV is observed directly. The cluster size-dependent population of these states in the expanding nanoplasma follows the well-known bottleneck model. The results support previous findings and highlight the important role of Rydberg states in the energetics and dynamics of laser-generated nanoplasma.

Femtosecond transient soft X-ray absorption spectroscopy (XAS) is a very promising technique that can be employed at X-ray free-electron lasers (FELs) to investigate out-of-equilibrium dynamics for material and energy research. Here, a dedicated setup for soft X-rays available at the Spectroscopy and Coherent Scattering (SCS) instrument at the European X-ray Free-Electron Laser (European XFEL) is presented. It consists of a beam-splitting off-axis zone plate (BOZ) used in transmission to create three copies of the incoming beam, which are used to measure the transmitted intensity through the excited and unexcited sample, as well as to monitor the incoming intensity. Since these three intensity signals are detected shot by shot and simultaneously, this setup allows normalized shot-by-shot analysis of the transmission. For photon detection, an imaging detector capable of recording up to 800 images at 4.5 MHz frame rate during the FEL burst is employed, and allows a photon-shot-noise-limited sensitivity to be approached. The setup and its capabilities are reviewed as well as the online and offline analysis tools provided to users.

Here, we use x-rays to create and probe quantum coherence in the photoionized amino acid glycine. The outgoing photoelectron leaves behind the cation in a coherent superposition of quantum mechanical eigenstates. Delayed x-ray pulses track the induced coherence through resonant x-ray absorption that induces Auger decay and by photoelectron emission from sequential double photoionization. Sinusoidal temporal modulation of the detected signal at early times (0 to 25 fs) is observed in both measurements. Advanced ab initio many-electron simulations allow us to explain the first 25 fs of the detected coherent quantum evolution in terms of the electronic coherence. In the kinematically complete x-ray absorption measurement, we monitor its dynamics for a period of 175 fs and observe an evolving modulation that may implicate the coupling of electronic to vibronic coherence at longer time scales. Our experiment provides a direct support for the existence of long-lived electronic coherence in photoionized biomolecules.

The pulse intensity from X-ray free-electron lasers (FELs) can create extreme excitation densities in solids, entering the regime of non-linear X-ray-matter interactions. We show L3-edge absorption spectra of metallic nickel thin films with fluences entering a regime where several X-ray photons are incident per absorption cross-section. Main features of the observed non-linear spectral changes are described with a predictive rate model for electron population dynamics during the pulse, utilizing a fixed density of states and tabulated ground-state properties.

High-power, high-energy, ultrashort, mid-infrared (MID-IR) laser systems operating at high repetition rates are of considerable interest for many science applications, such as coherent vibrational spectroscopy, label-free imaging, time-resolved pump-probe and high-harmonic generation studies. We developed an optical parametric chirped-pulse amplifier (OPCPA) system employing a difference-frequency generation in a lithium gallium sulfide nonlinear crystal in the final amplifier stage, which provides in principle the possibility for passive carrier-envelop-phase (CEP) stability. The OPCPA efficiently down-converts a 1 μm 200 μJ Yb-YAG pump pulse into the MID-IR spectral range generating μJ-level pulses at a repetition rate of 200 kHz. Two modes of operations providing complimentary MID-IR pulse properties are presented. Depending on the envisaged application, one can switch between (a) a wavelength-tunable (4.2–11 μm) source and (b) a broadband source centered at ≈8.5 μm by controlling the group-delay dispersion of the signal pulse. The broadband, high-energy MID-IR pulses have a short pulse duration of 74±2 fs, which corresponds to only ≈3 optical cycles at the central wavelength of 8.5 μm.

We present a versatile high repetition rate, optical-parametric chirped-pulse amplifier system (OPCPA) in combination with a high-harmonic-generation (HHG) source. Tuning of the fundamental OPCPA driver wavelength allows for high harmonic generation within the full range between 25 and 50 eV. All energies between two adjacent odd harmonics can be addressed, making the system a powerful, gaplessly tunable extreme-ultraviolet (XUV) light source for spectroscopy.

Interferometric pump-probe experiments in the extreme ultraviolet (XUV) domain are experimentally very challenging due to the high phase stability required between the XUV pulses. Recently, an efficient phase stabilization scheme was introduced for seeded XUV free electron lasers (FELs) combining shot-to-shot phase modulation with lock-in detection. This method stabilized the seed laser beampath on the fundamental ultraviolet wavelength to a high degree. Here, we extend this scheme including the stabilization of the XUV beampath, incorporating phase fluctuations from the FEL high gain harmonic generation process. Our analysis reveals a clear signal improvement with the new method compared to the previous stabilization scheme.

In the present contribution, we use x-rays to monitor charge-induced chemical dynamics in the photoionized amino acid glycine with femtosecond time resolution. The outgoing photoelectron leaves behind the cation in a coherent superposition of quantum mechanical eigenstates. Delayed x-ray pulses track the induced coherence through resonant x-ray absorption that induces Auger decay. Temporal modulation of the Auger electron signal correlated with specific ions is observed, which is governed by the initial electronic coherence and subsequent vibronic coupling to nuclear degrees of freedom. In the time-resolved x-ray absorption measurement, we monitor the time-frequency spectra of the resulting many-body quantum wave packets for a period of 175 fs along different reaction coordinates. Our experiment proves that by measuring specific fragments associated with the glycine dication as a function of the pump-probe delay, one can selectively probe electronic coherences at early times associated with a few distinguishable components of the broad electronic wave packet created initially by the pump pulse in the cation. The corresponding coherent superpositions formed by subsets of electronic eigenstates and evolving along parallel dynamical pathways show different phases and time periods in the range of ( − 0.3 ± 0.1 ) π ≤ ϕ ≤ ( 0.1 ± 0.2 ) π and 18.2 − 1.4 + 1.7 ≤ T ≤ 23.9 − 1.1 + 1.2 fs. Furthermore, for long delays, the data allow us to pinpoint the driving vibrational modes of chemical dynamics mediating charge-induced bond cleavage along different reaction coordinates.

Femtosecond extreme ultraviolet wave packet interferometry (XUV-WPI) was applied to study resonant interatomic Coulombic decay (ICD) in the HeNe dimer. The high demands on phase stability and sensitivity for vibronic XUV-WPI of molecular-beam targets are met using an XUV phase-cycling scheme. The detected quantum interferences exhibit vibronic dephasing and rephasing signatures along with an ultrafast decoherence assigned to the ICD process. A Fourier analysis reveals the molecular absorption spectrum with high resolution. The demonstrated experiment shows a promising route for the real-time analysis of ultrafast ICD processes with both high temporal and high spectral resolution.

Controlling the temporal and spectral properties of ultrashort laser pulses in the visible and near-infrared spectral range by means of a femtosecond pulse-shaping device is a powerful tool with many applications in ultrafast spectroscopy. A major and successful concept is known as the 4f design, which has a symmetric zero-dispersion-compressor geometry. Most 4f pulse shapers rely on using transmissive optics in their beam path limiting the operational wavelength ranges. In the present contribution, we use an all-reflective shaping setup to generate a phase-locked 266 nm double pulse to benchmark its performance in the limit of short wavelengths. The setup comprises the complete spectral amplitude and phase diagnostics for quantitative analysis of the pulse properties before and after the shaper using the technique of frequency-resolved optical gating. The measured time–frequency spectra are in good agreement with optical simulations. The geometry and hardware of the device including the optical components are designed, such that all harmonics of the deep UV pulses travel the same path, giving the instrument the ability to work with soft X-ray pulses, under vacuum conditions, down to the few-nanometer wavelength scale.

A review of the thermal parameters of Li-based nonlinear crystals is presented and preliminary results demonstrate a 8 µm laser system with 2 µJ at 200 kHz supporting a Fourier limit of under 100 fs.