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Dark field x-ray microscopy (DXFM) can visualize microstructural distortions in bulk crystals. Using the femtosecond x-ray pulses generated by x-ray free-electron lasers (XFELs), DFXM can achieve sub-μm spatial resolution and <100 fs time resolution simultaneously. In this paper, we demonstrate ultrafast DFXM measurements at the European XFEL to visualize an optically driven longitudinal strain wave propagating through a diamond single crystal. We also present two DFXM scanning modalities that are new to the XFEL sources: spatial 3D and 2D axial-strain scans with sub-μm spatial resolution. With this progress in XFEL-based DFXM, we discuss new opportunities to study multi-timescale spatiotemporal dynamics of microstructures. [ABSTRACT FROM AUTHOR]

X-ray self-heating is a common by-product of X-ray Free Electron Laser (XFEL) techniques that can affect targets, optics, and other irradiated materials. Diagnosis of heating and induced changes in samples may be performed using the x-ray beam itself as a probe. However, the relationship between conditions created by and inferred from x-ray irradiation is unclear and may be highly dependent on the material system under consideration. Here, we report on a simple case study of a titanium foil irradiated, heated, and probed by a MHz XFEL pulse train at 18.1 keV delivered by the European XFEL using measured x-ray diffraction to determine temperature and finite element analysis to interpret the experimental data. We find a complex relationship between apparent temperatures and sample temperature distributions that must be accounted for to adequately interpret the data, including beam averaging effects, multivalued temperatures due to sample phase transitions, and jumps and gaps in the observable temperature near phase transformations. The results have implications for studies employing x-ray probing of systems with large temperature gradients, particularly where these gradients are produced by the beam itself. Finally, this study shows the potential complexity of studying nonlinear sample behavior, such as phase transformations, where biasing effects of temperature gradients can become paramount, precluding clear observation of true transformation conditions. [ABSTRACT FROM AUTHOR]

Here, we investigate the hypothesis that despite the existence of at least two high-density amorphous ices, only one high-density liquid state exists in water. We prepared a very-high-density amorphous ice (VHDA) sample and rapidly increased its temperature to around 205 ± 10 K using laser-induced isochoric heating. This temperature falls within the so-called "no-man's land" well above the glass-liquid transition, wherein the IR laser pulse creates a metastable liquid state. Subsequently, this high-density liquid (HDL) state of water decompresses over time, and we examined the time-dependent structural changes using short x-ray pulses from a free electron laser. We observed a liquid–liquid transition to low-density liquid water (LDL) over time scales ranging from 20 ns to 3 μs, consistent with previous experimental results using expanded high-density amorphous ice (eHDA) as the initial state. In addition, the resulting LDL derived both from VHDA and eHDA displays similar density and degree of inhomogeneity. Our observation supports the idea that regardless of the initial annealing states of the high-density amorphous ices, the same HDL and final LDL states are reached at temperatures around 205 K. [ABSTRACT FROM AUTHOR]

The development and technological applications of molecular spin systems require versatile experimental techniques to characterize and control their static and dynamic magnetic properties. In the latter case, bulk spectroscopic and magnetometric techniques, such as AC magnetometry and pulsed electron paramagnetic resonance, are usually employed, showing high sensitivity, wide dynamic range, and flexibility. They are based on creating a nonequilibrium state either by changing the magnetic field or by applying resonant microwave radiation. Another possible source of perturbation is a laser pulse that rapidly heats the sample. This approach has proven to be one of the most useful techniques for studying the kinetics and mechanism of chemical and biochemical reactions. Inspired by these works, we propose an inductive detection of temperature-induced magnetization dynamics as applied to the study of molecular spin systems and describe the general design and construction of a particular induction probehead, taking into account the constraints imposed by the cryostat and electromagnet. To evaluate the performance, several coordination compounds of VO2+, Co2+, and Dy3+ were investigated using low-energy pulses of a terahertz free electron laser of the Novosibirsk free electron laser facility as a heat source. All measured magnetization dynamics were qualitatively or quantitatively described using a proposed basic theoretical model and compared with the data obtained by alternating current magnetometry. Based on the results of the research, the possible scope of applications of inductive detection and its advantages and disadvantages in comparison with standard methods are discussed. [ABSTRACT FROM AUTHOR]

We describe a method to compute photon–matter interaction and atomic dynamics with x-ray lasers using a hybrid code based on classical molecular dynamics and collisional-radiative calculations. The forces between the atoms are dynamically determined based on changes to their electronic occupations and the formation of a free electron cloud created from the irradiation of photons in the x-ray spectrum. The rapid transition from neutral solid matter to dense plasma phase allows the use of screened potentials, reducing the number of non-bonded interactions. In combination with parallelization through domain decomposition, the hybrid code handles large-scale molecular dynamics and ionization. This method is applicable for large enough samples (solids, liquids, proteins, viruses, atomic clusters, and crystals) that, when exposed to an x-ray laser pulse, turn into a plasma in the first few femtoseconds of the interaction. We present four examples demonstrating the applicability of the method. We investigate the non-thermal heating and scattering of bulk water and damage-induced dynamics of a protein crystal using an x-ray pump–probe scheme. In both cases, we compare to the experimental data. For single particle imaging, we simulate the ultrafast dynamics of a methane cluster exposed to a femtosecond x-ray laser. In the context of coherent diffractive imaging, we study the fragmentation as given by an x-ray pump–probe setup to understand the evolution of radiation damage in the time range of hundreds of femtoseconds. [ABSTRACT FROM AUTHOR]

X-ray free electron laser (XFEL) sources coupled to high-power laser systems offer an avenue to study the structural dynamics of materials at extreme pressures and temperatures. The recent commissioning of the DiPOLE 100-X laser on the high energy density (HED) instrument at the European XFEL represents the state-of-the-art in combining x-ray diffraction with laser compression, allowing for compressed materials to be probed in unprecedented detail. Here, we report quantitative structural measurements of molten Sn compressed to 85(5) GPa and ∼ 3500 K. The capabilities of the HED instrument enable liquid density measurements with an uncertainty of ∼ 1 % at conditions which are extremely challenging to reach via static compression methods. We discuss best practices for conducting liquid diffraction dynamic compression experiments and the necessary intensity corrections which allow for accurate quantitative analysis. We also provide a polyimide ablation pressure vs input laser energy for the DiPOLE 100-X drive laser which will serve future users of the HED instrument. [ABSTRACT FROM AUTHOR]

Wave packet interferometry with vacuum ultraviolet light has been used to probe a complex region of the electronic spectrum of molecular nitrogen, N2. Wave packets of Rydberg and valence states were excited by using double pulses of vacuum ultraviolet (VUV), free-electron-laser (FEL) light. These wave packets were composed of contributions from multiple electronic states with a moderate principal quantum number (n ∼ 4–9) and a range of vibrational and rotational quantum numbers. The phase relationship of the two FEL pulses varied in time, but as demonstrated previously, a shot-by-shot analysis allows the spectra to be sorted according to the phase between the two pulses. The wave packets were probed by angle-resolved photoionization using an infrared pulse with a variable delay after the pair of excitation pulses. The photoelectron branching fractions and angular distributions display oscillations that depend on both the time delays and the relative phases of the VUV pulses. The combination of frequency, time delay, and phase selection provides significant control over the ionization process and ultimately improves the ability to analyze and assign complex molecular spectra. [ABSTRACT FROM AUTHOR]

Time-Resolved Serial Femtosecond Crystallography (TR-SFX) conducted at X-ray Free Electron Lasers (XFELs) has become a powerful tool for capturing macromolecular structural movies of light-initiated processes. As the capabilities of XFELs advance, we anticipate that a new range of coherent control and structural Raman measurements will become achievable. Shorter optical and x-ray pulse durations and increasingly more exotic pulse regimes are becoming available at free electron lasers. Moreover, with high repetition enabled by the superconducting technology of European XFEL (EuXFEL) and Linac Coherent Light Source (LCLS-II) , it will be possible to improve the signal-to-noise ratio of the light-induced differences, allowing for the observation of vibronic motion on the sub-Angstrom level. To predict and assign this coherent motion, which is measurable with a structural technique, new theoretical approaches must be developed. In this paper, we present a theoretical density matrix approach to model the various population and coherent dynamics of a system, which considers molecular system parameters and excitation conditions. We emphasize the use of the Wigner transform of the time-dependent density matrix, which provides a phase space representation that can be directly compared to the experimental positional displacements measured in a TR-SFX experiment. Here, we extend the results from simple models to include more realistic schemes that include large relaxation terms. We explore a variety of pulse schemes using multiple model systems using realistic parameters. An open-source software package is provided to perform the density matrix simulation and Wigner transformations. The open-source software allows us to define any arbitrary level schemes as well as any arbitrary electric field in the interaction Hamiltonian. [ABSTRACT FROM AUTHOR]

X-ray-induced carrier dynamics in silicon and gallium arsenide were investigated through intensity variations of transmitted terahertz (THz) pulses in the pico- to microsecond timescale with x-ray free-electron laser and synchrotron radiation. We observed a steep reduction in THz transmission with a picosecond scale due to the x-ray-induced carrier generation, followed by a recovery on a nano- to microsecond scale caused by the recombination of carriers. The rapid response in the former process is applicable to a direct determination of temporal overlap between THz and x-ray pulses for THz pump–x-ray probe experiments with an accuracy of a few picoseconds. [ABSTRACT FROM AUTHOR]

The article discusses the contributions of John Hopfield and Geoffrey Hinton to artificial neural networks, leading to advancements in artificial intelligence technology. It also recognizes the late Mr. Guangzhao in Chinese science and Prof. Rohini Godbole in Indian collider physics, emphasizing gender equity in STEM. The Division of Plasma Physics (DPP) activities, including conferences and awards, are outlined, with the 2023 AAPPS-DPP conference awarding young researchers in plasma physics. The RMPP journal dedicated to plasma physics has been growing steadily since 2017, and the 2024 AAPPS-APCTP C. N. Yang Awards honored three young scholars for their physics contributions. The text also highlights achievements of physicists worldwide and initiatives by physics societies. [Extracted from the article]

Disulfide bonds are ubiquitous molecular motifs that influence the tertiary structure and biological functions of many proteins. Yet, it is well known that the disulfide bond is photolabile when exposed to ultraviolet C (UVC) radiation. The deep-UV-induced S-S bond fragmentation kinetics on very fast timescales are especially pivotal to fully understand the photostability and photodamage repair mechanisms in proteins. In 1,2-dithiane, the smallest saturated cyclic molecule that mimics biologically active species with S-S bonds, we investigate the photochemistry upon 200-nm excitation by femtosecond time-resolved x-ray scattering in the gas phase using an x-ray free electron laser. In the femtosecond time domain, we find a very fast reaction that generates molecular fragments with one and two sulfur atoms. On picosecond and nanosecond timescales, a complex network of reactions unfolds that, ultimately, completes the sulfur dissociation from the parent molecule. [ABSTRACT FROM AUTHOR]

Ultraintensity isolated zeptosecond pulses (ZPs) can be generated by an attosecond x-ray free-electron laser pulse normally incident on ultradense plasma slabs via the coherent bremsstrahlung (CB) regime in the transmission direction. In the unique CB regime, only one forwardly moving primary relativistic electron sheet (RES) contributes to the transmitted radiation, while the secondary RESs move in the reflection direction. The primary RES is accelerated to ultrarelativistic velocity with several multiple accelerations due to the charge compensation effect from the trajectory crossing between primary RES and secondary RES, then decelerated subsequently and eventually emits an ultraintensity isolated half-cycle ZP. The ZP has an intensity of ∼ 7.81 × 10 22 W / cm 2 , and a duration of 650 zs , and a power of ∼ 2.45 × 10 15 W that reaches the petawatt level. The x-ray laser pulse-driven petawatt ZP emission mechanism may open the intra-nuclear dynamics and the high-field QED in vacuum studies. [ABSTRACT FROM AUTHOR]

The Linac Coherent Light Source (LCLS) is the world's first x-ray free electron laser. It is a scientific user facility operated by the SLAC National Accelerator Laboratory, at Stanford, for the U.S. Department of Energy. As beam time at LCLS is extremely valuable and limited, experimental efficiency—getting the most high quality data in the least time—is critical. Our overall project employs cognitive engineering methodologies with the goal of improving experimental efficiency and increasing scientific productivity at LCLS by refining experimental interfaces and workflows, simplifying tasks, reducing errors, and improving operator safety and stress. Here, we describe a multi-agent, multi-scale computational cognitive interaction model of instrument operations at LCLS. Our model simulates the aspects of human cognition at multiple cognitive and temporal scales, ranging from seconds to hours, and among agents playing multiple roles, including instrument operator, real time data analyst, and experiment manager. The model can roughly predict impacts stemming from proposed changes to operational interfaces and workflows. Example results demonstrate the model's potential in guiding modifications to improve operational efficiency. We discuss the implications of our effort for cognitive engineering in complex experimental settings and outline future directions for research. The model is open source, and the videos of the supplementary material provide extensive detail. [ABSTRACT FROM AUTHOR]

Free-Electron Laser in Hamburg (FLASH), first launched in 2005, was the first free-electron laser that provided ultrashort radiation pulses in extreme ultraviolet and soft X-ray spectral range. In 2017, it was decided to improve the existing FLASH facility within the FLASH2020+ project, which led to upgrading the existing linac with variable gap tunable undulators in the FLASH1 line and refurbishing two cryomodules to achieve a beam energy increase to 1.35 GeV. It was also a perfect opportunity to completely redesign and rebuild the radio frequency (RF) phase reference generation and distribution system. This paper presents the design and parameters of new, custom-made phase reference signal generation and distribution modules, successfully installed in FLASH. These are the main oscillator, the RF distribution module, and the frequency conversion modules. The new instrumentation presents a significant improvement in terms of RF reference signal parameters, state-of-the-art phase noise performance (an improvement in the total jitter of the 1.3 GHz RF signal from 55.9 fs to 10.7 fs in the integration range from 10 Hz to 1 MHz), module compactness (size reduction from three fully occupied rack cabinets to four 19″ modules only), and serviceability. The presented Main Oscillator system design is foreseen for easy modifications, making it suitable for applications in other accelerator facilities or hardware platforms. [ABSTRACT FROM AUTHOR]

Oxygen vacancies in indium tin oxide (ITO) thin films provide a direct route to effectively tune the free electron density and thereby, controlling the epsilon-near-zero (ENZ) cut-off wavelength, the wavelength at which the real part of permittivity crosses zero of the permittivity axis. In this report, oxygen vacancies in pulsed laser deposited ITO thin films are systematically tuned using different background gases (O 2 , N 2 , Ar, and He). ENZ cut-offs are observed for the films deposited under He and Ar gases. In contrast, no such cut-offs are observed in the case of other two gases. An ITO thin film deposited under He gas exhibits deeper resonance signal than the one deposited under Ar gas. As expected, no such dip in the resonance spectra is observed for the films deposited under O 2 and N 2 gases. This observation is directly correlated to the change in the number of oxygen vacancies under different ambient gases. A modified transfer matrix method which incorporates surface roughness as an effective medium layer is developed to describe the experimentally observed resonance spectra numerically. Angular invariancy of ENZ plasmon resonance and the difference in absorption values for ITO films deposited under different gases is understood in terms of local field intensity enhancement factor. The study presented here will certainly be very useful in understanding the ENZ plasmon resonance phenomena as a whole. Additionally, ITO films deposited under an inert gas environment could be excellent material platforms for realizing several exotic ENZ applications. [ABSTRACT FROM AUTHOR]

Models attempting an analytical description of free-electron laser (FEL) devices have been proposed in the past. They provided interesting results, leading either to a deeper understanding of the FEL dynamics and to semi-analytical formulae, useful for the preliminary design of self amplified spontaneous emission and oscillator FELs. Most of these models work well until the level of mild saturation. In this paper, we comment on the so-called logistic model and a more recent analysis describing the FEL evolution in terms of Jacobi elliptic functions. Both models are shown to be suited to describe the evolution from the low signal to the onset of saturation. We attempt therefore an extension of these theoretical formulations using a delayed logistic model, capable of including characteristic features like the post saturation power oscillations. [ABSTRACT FROM AUTHOR]

Elucidating the mutual effects between the different volatile organic compounds (VOCs) is crucial for comprehending the formation mechanism of atmospheric secondary organic aerosols (SOA). Here, the mixed VOCs experiments of isoprene and Δ3-carene/β-caryophyllene were carried out in the presence of O 3 using an indoor smog chamber. The suppression effect of isoprene was recognized by the scanning mobility particle sizer spectrometer, online vacuum ultraviolet free electron laser (VUV-FEL) photoionization aerosol mass spectrometry, and quantum chemical calculations. The results indicate that the suppression effect of isoprene on the ozonolysis of Δ3-carene and β-caryophyllene shows fluctuating and monotonous trends, respectively. The carbon content of the precursor could be the main factor for regulating the strength of the suppression effect. Plausible structures and formation mechanisms of several new products generated from the single VOC precursor and VOC-cross-reaction are proposed, which enrich the category of VOC oxidation products. Meanwhile, a new dimerization mechanism of the RO 2 + R'O 2 reaction is suggested, which offers an intriguing perspective on the gas phase formation process of particle phase accretion products. The present findings provide valuable insights into clarifying the pivotal roles played by isoprene in the interplay between different VOCs and understanding of SOA formation mechanisms of VOC mixtures, especially nearby the emission origins. [Display omitted] [ABSTRACT FROM AUTHOR]

Femtosecond laser excitation of crystal materials can produce coherent longitudinal acoustic phonons (CLAPs), which possess the capability to interact with various quasiparticles and influence their dynamics. The manipulation of CLAPs' behavior is thus of significant interest for potential applications, particularly in achieving ultrafast modulations of material properties. In this study, we present our findings on the propagation of laser-induced CLAPs at thin-film interfaces and heterojunctions using ultrafast optical reflectivity and ultrafast x-ray diffraction measurements. We observe that CLAPs can efficiently propagate from a LaMnO3 thin-film to its SrTi O 3 substrate due to the matching of their acoustic impedance, and the oscillation period increases from 54 to 105 GHz. In contrast, in ultrafast x-ray diffraction experiments, we discover that CLAPs are partially confined within an Au (111) thin film due to the mismatch of acoustic impedance with the substrates, leading to an oscillation period of 122 ps. However, interestingly, when examining L a 0.7 C a 0.175 S r 0.125 Mn O 3 / B a 0.5 S r 0.5 Ti O 3 bilayers, no oscillations are observed due to the favorable impedance matching between the layers. Our findings demonstrate that acoustic impedance can serve as an effective means to control coherent phonons in nanometer-thin films and may also play a crucial role in phonon engineering at interfaces or heterostructures. [ABSTRACT FROM AUTHOR]

A new diamond anvil cell experimental approach has been implemented at the European x-ray Free Electron Laser, combining pulsed laser heating with MHz x-ray diffraction. Here, we use this setup to determine liquidus temperatures under extreme conditions, based on the determination of time-resolved crystallization. The focus is on a Fe-Si-O ternary system, relevant for planetary cores. This time-resolved diagnostic is complemented by a finite-element model, reproducing temporal temperature profiles measured experimentally using streaked optical pyrometry. This model calculates the temperature and strain fields by including (i) pressure and temperature dependencies of material properties, and (ii) the heat-induced thermal stress, including feedback effect on material parameter variations. Making our model more realistic, these improvements are critical as they give 7000 K temperature differences compared to previous models. Laser intensities are determined by seeking minimal deviation between measured and modeled temperatures. Combining models and streak optical pyrometry data extends temperature determination below detection limit. The presented approach can be used to infer the liquidus temperature by the appearance of SiO 2 diffraction spots. In addition, temperatures obtained by the model agree with crystallization temperatures reported for Fe–Si alloys. Our model reproduces the planetary relevant experimental conditions, providing temperature, pressure, and volume conditions. Those predictions are then used to determine liquidus temperatures at experimental timescales where chemical migration is limited. This synergy of novel time-resolved experiments and finite-element modeling pushes further the interpretation capabilities in diamond anvil cell experiments. [ABSTRACT FROM AUTHOR]

Innovative, low-loss, and compact optical systems are essential to meet the experimental requirements of emerging novel radiation sources. The microchannel plate (MCP), a metamaterial-based optical device, shows promising potential for shaping, condensing, and focusing soft x-ray radiation at synchrotron radiation (SR) facilities. This study highlights the impact of MCP optical devices on SR beam condensing capability and their sensitivity to the degree of coherence by investigating the profile of transmitted beams through single and double MCP optical devices. Transmitted diffraction patterns of soft x-ray SR radiation change with energy and radiation modes. At 92 eV, the double MCP-based device affects the beam divergence and degree of coherence more than the single MCP. Moreover, the double MCP device shows potential as a condensing optics at shorter wavelengths, i.e., 480 eV. Experiments were performed at the available end-station of the Circular Polarization beamline at the Elettra synchrotron facility in Trieste, using a high-vacuum chamber with a hexapod system, providing the precise movement necessary to align these diffractive optics. The findings contribute to the development of innovative optical systems for SR and free-electron laser beamlines, paving the way for advanced experiments in spectroscopy, microscopy, and imaging in a wide energy range. [ABSTRACT FROM AUTHOR]

Experiments accessing extreme conditions at x-ray free electron lasers (XFELs) involve rapidly evolving conditions of temperature. Here, we report time-resolved, direct measurements of temperature using spectral streaked optical pyrometry of x-ray and optical laser-heated states at the High Energy Density instrument of the European XFEL. This collection of typical experiments, coupled with numerical models, outlines the reliability, precision, and meaning of time dependent temperature measurements using optical emission at XFEL sources. Dynamic temperatures above 1500 K are measured continuously from spectrally- and temporally-resolved thermal emission at 450–850 nm, with time resolution down to 10–100 ns for 1–200 μ s streak camera windows, using single shot and integrated modes. Targets include zero-pressure foils free-standing in air and in vacuo, and high-pressure samples compressed in diamond anvil cell multi-layer targets. Radiation sources used are 20-fs hard x-ray laser pulses at 17.8 keV, in single pulses or 2.26 MHz pulse trains of up to 30 pulses, and 250-ns infrared laser single pulses. A range of further possibilities for optical measurements of visible light in x-ray laser experiments using streak optical spectroscopy are also explored, including for the study of x-ray induced optical fluorescence, which often appears as background in thermal radiation measurements. We establish several scenarios where combined emissions from multiple sources are observed and discuss their interpretation. Challenges posed by using x-ray lasers as non-invasive probes of the sample state are addressed. [ABSTRACT FROM AUTHOR]

Alanine racemase (Alr) catalyzes the pyridoxal 5′-phosphate (PLP)-dependent racemization between l- and d-alanine in bacteria. Owing to the potential interest in targeting Alr for antibacterial drug development, several studies have determined the structures of Alr from different species, proposing models for the reaction mechanism. Insights into its reaction dynamics may be conducive to a better understanding of the Alr reaction mechanism. In this study, we determined the structures of the apo and reaction states of Bacillus subtilis Alr (BsAlr) at room temperature using a fixed-target based X-ray free-electron laser. The 2.3 Å resolution structures revealed the alanine substrate or intermediate in various positions at the active site. Conformational change between the N- and C-terminal domains of BsAlr expanded the entryway for substrate binding. In the reaction state of BsAlr, two main alanine binding states were observed: one alanine molecule is positioned away from PLP, whereas the other alanine molecule is covalently bonded to PLP. These structures might represent the dynamic states of the substrate for entrance into, reaction with, or exit from the active site. Our approach provides a simple and rapid method for elucidating the intermediate structure of Alr, which can be expanded to other enzymes. [ABSTRACT FROM AUTHOR]

By employing the stabilizer in the supersonic gas nozzle to produce the plasma density profile with a sharp downramp, we have experimentally demonstrated highly stable electron beam acceleration based on the shock injection mechanism in laser wakefield acceleration with the use of a compact Ti:sapphire laser. A quasi-monoenergetic electron beam with a peak energy of 315 MeV ± 12.5 MeV per shot is generated. The electron pointing fluctuations are less than 1 mrad, which is a significant improvement over previous results. This is due to the precise control of the target density distribution and the relative distance between the shock and the laser focal position. The Particle-in-cell simulations demonstrate the sensitivity of electron acceleration to the target profile, while the computational fluid dynamics prove the stabilizer's effect on gas formation. Further developments of this scheme have the potential to deliver a high repetition rate gas target. The corresponding reproducibility of the accelerated electron beam paves the way for the realisation of compact laser plasma accelerators and the potential application of free electron lasers. [ABSTRACT FROM AUTHOR]

Photosystem II (PSII) catalyzes light-driven water oxidation that releases dioxygen into our atmosphere and provides the electrons needed for the synthesis of biomass. The catalysis occurs in the oxygen-evolving oxo-manganese-calcium (Mn4O5Ca) cluster that drives the oxidation and deprotonation of substrate water molecules leading to the O2 formation. However, despite recent advances, the mechanism of these reactions remains unclear and much debated. Here, we show that the light-driven Tyr161D1 (Yz) oxidation adjacent to the Mn4O5Ca cluster, decreases the barrier for proton transfer from the putative substrate water molecule (W3/Wx) to Glu310D2, accessible to the luminal bulk. By combining hybrid quantum/classical (QM/MM) free energy calculations with atomistic molecular dynamics simulations, we probe the energetics of the proton transfer along the Cl1 pathway. We demonstrate that the proton transfer occurs via water molecules and a cluster of conserved carboxylates, driven by redox-triggered electric fields directed along the pathway. Glu65D1 establishes a local molecular gate that controls the proton transfer to the luminal bulk, while Glu312D2 acts as a local proton storage site. The identified gating region could be important in preventing backflow of protons to the Mn4O5Ca cluster. The structural changes, derived here based on the dark-state PSII structure, strongly support recent time-resolved X-ray free electron laser data of the S3 → S4 transition (Bhowmick et al. Nature 617, 2023) and reveal the mechanistic basis underlying deprotonation of the substrate water molecules. Our findings provide insight into the water oxidation mechanism of PSII and show how the interplay between redox-triggered electric fields, ion-pairs, and hydration effects control proton transport reactions. [ABSTRACT FROM AUTHOR]

The editorial in "Frontiers in Physics" discusses the challenges and advancements in developing detectors for photon science, focusing on X-ray imaging detectors and sensors. The text highlights the need for detectors to meet the performance increase of new photon sources like Free Electron Lasers and Diffraction-Limited Storage Rings. It also addresses the challenges of data reduction and processing, as well as operational complexities in running imaging systems at photon science facilities. The editorial emphasizes the importance of simplifying system integration and calibration to enhance user interest and data quality in imaging detectors for photon science. [Extracted from the article]

A reliable characterization of x-ray pulses is critical to optimally exploit advanced photon sources, such as free-electron lasers. In this paper, we present a method based on machine learning, the virtual spectrometer, that improves the resolution of non-invasive spectral diagnostics at the European XFEL by up to 40%, and significantly increases its signal-to-noise ratio. This improves the reliability of quasi-real-time monitoring, which is critical to steer the experiment, as well as the interpretation of experimental outcomes. Furthermore, the virtual spectrometer streamlines and automates the calibration of the spectral diagnostic device, which is otherwise a complex and time-consuming task, by virtue of its underlying detection principles. Additionally, the provision of robust quality metrics and uncertainties enable a transparent and reliable validation of the tool during its operation. A complete characterization of the virtual spectrometer under a diverse set of experimental and simulated conditions is provided in the manuscript, detailing advantages and limits, as well as its robustness with respect to the different test cases. A reliable characterization of x-ray pulses is critical to optimally exploit advanced photon sources, such as free-electron lasers. The authors present a method based on machine learning which improves the resolution and signal-to-noise ratio of the non-invasive spectral diagnostics available at European XFEL, and streamlines its operation. [ABSTRACT FROM AUTHOR]

The primary and secondary fragmentation dynamics of iodobenzene following its ionization at 120 eV were determined using three-dimensional velocity map imaging and covariance analysis. Site-selective iodine 4d ionization was used to populate a range of excited polycationic parent states, which primarily broke apart at the carbon-iodine bond to produce I+ with phenyl or phenyl-like cations (C n H x + or C n H x 2 + , with n = 1 – 6 and x = 1 – 5). The molecular products were produced with varying degrees of internal excitation and dehydrogenation, leading to stable and unstable outcomes. This further allowed the secondary dynamics of C 6 H x 2 + intermediates to be distinguished using native-frame covariance analysis, which isolated these processes in their own centre-of-mass reference frames. The mass resolution of the imaging mass spectrometer used for these measurements enabled the primary and secondary reaction channels to be specified at the level of individual hydrogen atoms, demonstrating the ability of covariance analysis to comprehensively measure the competing fragmentation channels of aryl cations, including those involving intermediate steps. [ABSTRACT FROM AUTHOR]

Serial crystallography, which has been extensively developed in the past years, makes it possible to study dynamic processes occurring in protein molecules. The method is implemented at fourth-generation synchrotron sources or free electron lasers and it requires suspensions of microcrystals. It was demonstrated that small-angle X-ray scattering can be used to monitor the formation of such suspensions in crystallization conditions as exemplified by lysozyme. [ABSTRACT FROM AUTHOR]

Pump-probe excitation technique using mid-infrared free electron laser and Nd:YVO4 ps-laser from Kyoto University free electron laser facility was implied to selectively excite a Raman inactive phonon mode of a semiconductor single crystal sample. The LO3 phonon mode of strontium titanate was chosen and the MIR-FEL photon energy was adjusted to match the target phonon mode energy, which corresponded to a wavelength of 12.5 µm. Temporal and spatial overlapping of MIR-FEL pulses and probe laser pulses were performed and confirmed through sum frequency generation from ZnS cleartran®. Confirmation of the Raman forbidden mode excitation was achieved through the anti-Stokes hyper-Raman scattering (ASHRS) spectroscopy method. Successful excitation was observed at 5 K, where thermal excitation of all other phonon modes was suppressed. The recorded spectrum showed a signal that was red-shifted from 800 to around 761 cm−1. The broadened line width (FWHM) and the red-shifting phenomenon in the recorded result have been observed due to the restraint of the spectrometer slit width function and the intense irradiation of the picosecond laser for hyper-Raman scattering spectroscopy, which have also led to surface damage on the crystal sample. [ABSTRACT FROM AUTHOR]

We study the resonant processes of the excitation of weakly bound NeAr + ions in collisions with the free electrons of Ne/Ar mixture plasma under conditions typical of the active media of gas lasers and plasma-based UV radiation sources. The transitions leading to the population of charge transfer electronic terms are considered. Using an original theoretical approach developed recently, we study the dependences of the cross-sections of several competing resonant processes on the incident electron energy and the gas temperature of the plasma. The role of the continuous states of internuclear motion is discussed. We highlight the specific features of the processes considered that stem from the low binding energy of NeAr + ions and demonstrate that, in the weakly bound systems, the efficiencies of different charge transfer excitation channels differ greatly from those obtained for ions with moderate dissociation energies. [ABSTRACT FROM AUTHOR]

Short-lived core-ionized neon atoms were investigated by measuring under resonant Raman conditions the Auger decay following the excitation of a second core electron into a Rydberg state. Making use of intense and narrow bandwidth x-ray free-electron laser pulses, the photoexcitation spectrum of the femtosecond-lived Ne + 1 s 0 2 s 2 2 p 6 n p series was characterized. Energy position and lifetimes of the lower-lying Rydberg states were determined and the final state configurations following the decay of the Ne + 1 s 0 2 s 2 2 p 6 3 p double-core hole resonance were partially resolved. [ABSTRACT FROM AUTHOR]

We consider two cases of spontaneous anomalous Hall current. In a non-magnetic system with spin–orbit coupling (SOC), the applied bias results in the appearance of non-equilibrium magnetization and an anomalous Hall current. The latter demonstrates non-linear dependence on the applied bias. In a magnetic system with SOC, an anomalous current appears without applied bias. We perform the calculations in the framework of the free-electron model, whereas the common approach to this type of phenomenon is based on Berry connection. We demonstrate that anomalous currents acquire a measurable magnitude for reasonable model parameters. [ABSTRACT FROM AUTHOR]

Time-resolved serial crystallography at X-ray Free Electron Lasers offers the opportunity to observe ultrafast photochemical reactions at the atomic level. The technique has yielded exciting molecular insights into various biological processes including light sensing and photochemical energy conversion. However, to achieve sufficient levels of activation within an optically dense crystal, high laser power densities are often used, which has led to an ongoing debate to which extent photodamage may compromise interpretation of the results. Here we compare time-resolved serial crystallographic data of the bacteriorhodopsin K-intermediate collected at laser power densities ranging from 0.04 to 2493 GW/cm2 and follow energy dissipation of the absorbed photons logarithmically from picoseconds to milliseconds. Although the effects of high laser power densities on the overall structure are small, in the upper excitation range we observe significant changes in retinal conformation and increased heating of the functionally critical counterion cluster. We compare light-activation within crystals to that in solution and discuss the impact of the observed changes on bacteriorhodopsin biology. Time-resolved serial crystallography at XFELs reveals ultrafast photochemical reactions, but high laser densities can cause photodamage to biological samples. Here, the authors study the early K-intermediate in bacteriorhodopsin at high power, showing overall conformation remains robust over a wide range. [ABSTRACT FROM AUTHOR]

Angle-resolved photoelectron spectrometers with microchannel plate detectors and fast digitizer electronics are versatile and powerful devices for providing non-invasive single-shot photon diagnostics at a MHz repetition rate X-ray free-electron lasers. In this contribution, we demonstrate and characterize the performance of our two operational photoelectron spectrometers for the application of hard X-rays and soft X-rays as well as new automation tools and online data analysis that enable continuous support for machine operators and instrument scientists. Customized software has been developed for the real-time monitoring of photon beam polarization and spectral distribution both in single-color and two-color operation. Hard X-ray operation imposes specific design challenges due to poor photoionization cross-sections and very high photoelectron velocities. Furthermore, recent advancements in machine learning enable resolution enhancement by training the photoelectron spectrometer together with an invasive high-resolution spectrometer, which generates a response function model. [ABSTRACT FROM AUTHOR]

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 ≈ 1 K) and dense (ρ ≈ 108 cm−3) molecular beam with pulse durations up to 100 µs 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, the SQS and single particles, clusters, and biomolecules (SPB) instruments. This advanced controlled-molecules injection setup enables x-ray free-electron laser 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. [ABSTRACT FROM AUTHOR]

Context. Interstellar ices and their energetic processing play an important role in advancing the chemical complexity in space. Interstellar ices covering dust grains are intrinsically mixed, and it is assumed that physicochemical changes induced by energetic processing – triggered by photons, electrons, and ions – strongly depend on the content of the ice. Yet, the modelling of these complex mixed systems in experiments and theory is complicated. Aims. In this paper, we investigate the effect of infrared irradiation on a series of different molecules mixed with porous amorphous solid water (pASW) to study the release of vibrational energy in the hydrogen-bonding network of water as a function of mixing ratio and ice content. Particularly, we select mixtures of 20:1 H2O:X and 5:1 H2O:X with X=CO2, NH3, or CH4. Methods. Infrared radiation was supplied by the intense and tunable free electron laser (FEL) 2 at the HFML-FELIX facility. We monitored the structural changes in the interstellar ice analogue after resonant infrared excitation using Fourier-transform reflection absorption infrared (FT-RAIR) spectroscopy. Results. We observed that on-resonance irradiation at the OH-stretching vibration of pASW results in quantitatively identical changes compared to pure pASW for all investigated mixtures. The structural changes we observed closely resemble the previously reported local reordering. The 5:1 mixtures show weaker changes compared to pure pASW, with a decrease in strength from NH3 to CO2. Conclusions. Since the hydrogen-bonding network of pASW restructures similarly upon FEL irradiation, regardless of the mixing component, treating ice layers in models that simulate energy dissipation in the hydrogen-bonding network as pure H2O ice layers can be a justified approximation. Hence, complex systems might not always be necessary to describe the infrared energetic processing of ices. [ABSTRACT FROM AUTHOR]

The Chinese Academy of Engineering Physics Terahertz Free Electron Laser Facility (CAEP THz FEL, CTFEL) is the only high-average power free electron laser terahertz source based on superconducting accelerators in China. The update of the CTFEL is now undergoing and will expand the frequency range from 0.1–4.2 THz to 0.1–125 THz. Two experimental stations for material spectroscopy and biomedicine will be built. A high harmonic generation (HHG) lightsource based beamline at the material spectroscopy experimental station for time-resolved angle-resolved photoemission spectroscopy (ARPES) research will be constructed and the optical design is presented. The HHG lightsource covers the extreme ultraviolet (XUV) photon energy range of 20–50 eV. A Czerny–Turner monochromator with two plane gratings worked in conical diffraction configuration is employed to maintain the transmission efficiency and preserve the pulse time duration. The calculated beamline transmission efficiency is better than 5% in the whole photon energy range. To our knowledge, this is the first time in China to combine THz-infrared FEL with HHG light source, and this experimental station will be a powerful and effective instrument that will give new research opportunities in the future for users doing research on the dynamic evolution of the excited electron band structure of a material's surface. [ABSTRACT FROM AUTHOR]

Time-resolved x-ray crystallography (TR-X) at synchrotrons and free electron lasers is a promising technique for recording dynamics of molecules at atomic resolution. While experimental methods for TR-X have proliferated and matured, data analysis is often difficult. Extracting small, time-dependent changes in signal is frequently a bottleneck for practitioners. Recent work demonstrated this challenge can be addressed when merging redundant observations by a statistical technique known as variational inference (VI). However, the variational approach to time-resolved data analysis requires identification of successful hyperparameters in order to optimally extract signal. In this case study, we present a successful application of VI to time-resolved changes in an enzyme, DJ-1, upon mixing with a substrate molecule, methylglyoxal. We present a strategy to extract high signal-to-noise changes in electron density from these data. Furthermore, we conduct an ablation study, in which we systematically remove one hyperparameter at a time to demonstrate the impact of each hyperparameter choice on the success of our model. We expect this case study will serve as a practical example for how others may deploy VI in order to analyze their time-resolved diffraction data. [ABSTRACT FROM AUTHOR]

This study delves into the relatively uncharted territory of Above Threshold Ionization in atoms, triggered by intense X-ray radiation fields. At these frequencies, the energy of a single photon far exceeds the ionization potential of valence electrons in atoms and molecules. The conditions we examine are similar to those achievable with current or future free-electron laser facilities. Under such high-energy scenarios, the onset of strong field ionization requires a shift away from the traditional quasi-classical approach. Here, we present an analytical model to characterize how the field-free ionization potential, ponderomotive energy, and photon energy govern the transition to this regime, all accounted for by means of the Keldysh and Reiss parameters. We show that both of these parameters are needed to capture the onset of strong-field behavior due to both bound state and continuum state properties. At higher X-ray intensities, we find that ionization rates deviate from the linear intensity scaling expected from lowest order perturbative processes, corresponding to channel closure and higher-order photon absorption processes. This study explores Above Threshold Ionization in atoms induced by intense X-ray radiation fields, where photon energy surpasses the ionization potential of valence electrons. The authors demonstrate that both the Keldysh and Reiss parameters are essential to capture the onset of strong-field behavior, revealing deviations from weak-field intensity scaling at higher X-ray intensities. [ABSTRACT FROM AUTHOR]

The ultrashort and intense pulses of X-rays produced at X-ray free electron lasers (XFELs) have enabled unique experiments on the atomic level structure and dynamics of matter, with time-resolved studies permitted in the femto- and attosecond regimes. To fully exploit them, it is paramount to obtain a comprehensive understanding of the complex nonlinear interactions that can occur at such extreme X-ray intensities. Herein, we report on the experimental observation of a resonant double-core excitation scheme in N2, where two 1σ core-level electrons are resonantly promoted to unoccupied 1 π g * molecular orbitals by a single few-femtosecond broad-bandwidth XFEL pulse. The production of these neutral two-site double core hole states is evidenced through their characteristic decay channels, which are observed in good agreement with high-level theoretical calculations. Such multi-core excitation schemes, benefiting from the high interaction cross sections and state- and site-selective nature of resonant X-ray interactions, should be generally accessible in XFEL irradiated molecules, and provide interesting opportunities for chemical analysis and for monitoring ultrafast dynamic processes. XFELs can drive multicore-ionization/excitation processes in the fs timescale of typical core-hole lifetimes in molecules. This paper reports experimental evidence of a single XFEL-pulse-driven resonant double-core excitation mechanism, producing a neutral two-site double-core-hole state in the nitrogen molecule. [ABSTRACT FROM AUTHOR]

In this perspective article we propose and discuss a possible technique of in-depth material processing based on undersurface focusing of intense x-ray pulses. Currently, x-ray free-electron lasers can produce such intense x-ray pulses with femtosecond pulse durations, reaching intensities sufficiently high to cause ultrafast melting of a material after a single laser shot. Here, on the example of silicon crystal we will demonstrate that with a proper choice of pulse parameters and focusing parameters, the already existing nanofocusing setup has a capability to focus hard x rays down to several hundreds micrometers below the material surface. This can trigger the required structural modification in the focal point, without damaging the material above. Potential applications of the new technique are discussed. [ABSTRACT FROM AUTHOR]

Because the work function (WF) of the thermionic cathode of an electron gun is the primary factor for determining emission current density, the precise monitoring of the WF in actual operational conditions under high temperatures is essential for tracking the status of the cathode surface. We adjusted a theoretical model of quantum efficiency under high temperatures as proposed by R. H. Fowler to include the final energy state in the photoexcitation process. This modification is necessary for estimating the WF precisely with the measurement results obtained by photoelectron yield spectroscopy using a tunable pulsed laser in the wavelength range from 410 to 709 nm. As the first step of the investigation, we conducted WF measurements of a single-crystal CeB6 cathode, which is employed for the SACLA x-ray free-electron laser. The WF of the unused fresh CeB6 was 2.44 ± 0.02 eV at a high temperature of 836 °C. Our future plans for WF measurements are also discussed below. [ABSTRACT FROM AUTHOR]

In ferromagnets, domain patterns can be controlled globally using magnetic fields or spin-polarized currents. In contrast, the local control of the magnetization on the nanometer length scale remains challenging. Here, we demonstrate how magnetic domain patterns in a Tm-doped yttrium iron garnet (Tm:YIG) thin film with perpendicular magnetic anisotropy can be permanently and locally imprinted by high intensity photon pulses of a hard x-ray transient grating (XTG). Micromagnetic simulations provide a qualitative understanding of the observed changes in the orientation of magnetic domains in Tm:YIG and XTG-induced changes. The presented results offer a route for the local manipulation of the magnetic state using hard XTG. [ABSTRACT FROM AUTHOR]

The linear radical cation of cyanoacetylene, HC3N+ (2Π), is not only of astrophysical interest, being the, so far undetected, cationic counterpart of the abundant cyanoaceteylene, but also of fundamental spectroscopic interest due to its strong spin–orbit and Renner–Teller interactions. Here, we present the first broadband vibrational action spectroscopic investigation of this ion through the infrared pre-dissociation (IRPD) method using a Ne tag. Experiments have been performed using the FELion cryogenic ion-trap instrument in combination with the FELIX free-electron lasers and a Laservision optical parametric oscillator/optical parametric amplifier system. The vibronic splitting patterns of the three interacting bending modes (ν5, ν6, ν7), ranging from 180 to 1600 cm−1, could be fully resolved revealing several bands that were previously unobserved. The associated Renner–Teller and intermode coupling constants have been determined by fitting an effective Hamiltonian to the experimental data, and the obtained spectroscopic constants are in reasonable agreement with previous photoelectron spectroscopy (PES) studies and ab initio calculations on the HC3N+ ion. The influence of the attached Ne atom on the infrared spectrum has been investigated by ab initio calculations at the RCCSD(T)-F12a level of theory, which strongly indicates that the discrepancies between the IRPD and PES data are a result of the effects of the Ne attachment. [ABSTRACT FROM AUTHOR]

The linear radical cation of cyanoacetylene, HC3N+ (2Π), is not only of astrophysical interest, being the, so far undetected, cationic counterpart of the abundant cyanoaceteylene, but also of fundamental spectroscopic interest due to its strong spin–orbit and Renner–Teller interactions. Here, we present the first broadband vibrational action spectroscopic investigation of this ion through the infrared pre-dissociation (IRPD) method using a Ne tag. Experiments have been performed using the FELion cryogenic ion-trap instrument in combination with the FELIX free-electron lasers and a Laservision optical parametric oscillator/optical parametric amplifier system. The vibronic splitting patterns of the three interacting bending modes (ν5, ν6, ν7), ranging from 180 to 1600 cm−1, could be fully resolved revealing several bands that were previously unobserved. The associated Renner–Teller and intermode coupling constants have been determined by fitting an effective Hamiltonian to the experimental data, and the obtained spectroscopic constants are in reasonable agreement with previous photoelectron spectroscopy (PES) studies and ab initio calculations on the HC3N+ ion. The influence of the attached Ne atom on the infrared spectrum has been investigated by ab initio calculations at the RCCSD(T)-F12a level of theory, which strongly indicates that the discrepancies between the IRPD and PES data are a result of the effects of the Ne attachment. [ABSTRACT FROM AUTHOR]

Linear-accelerator-based applications like x-ray free electron lasers, ultrafast electron diffraction, electron beam cooling, and energy recovery linacs use photoemission-based cathodes in photoinjectors for electron sources. Most of these photocathodes are typically grown as polycrystalline materials with disordered surfaces. In order to understand the mechanism of photoemission from such cathodes and completely exploit their photoemissive properties, it is important to develop a photoemission formalism that properly describes the subtleties of these cathodes. The Dowell–Schmerge (D–S) model often used to describe the properties of such cathodes gives the correct trends for photoemission properties like the quantum efficiency (QE) and the mean transverse energy (MTE) for metals; however, it is based on several unphysical assumptions. In the present work, we use Spicer's three-step photoemission formalism to develop a photoemission model that results in the same trends for QE and MTE as the D–S model without the need for any unphysical assumptions and is applicable to defective thin-film semiconductor cathodes along with metal cathodes. As an example, we apply our model to Cs 3 Sb thin films and show that their near-threshold QE and MTE performance is largely explained by the exponentially decaying defect density of states near the valence band maximum. [ABSTRACT FROM AUTHOR]