Ultrafast X-ray Research Articles

A predicted model-aided reconstruction algorithm for X-ray free-electron laser single-particle imaging.

Ultra-intense, ultra-fast X-ray free-electron lasers (XFELs) enable the imaging of single protein molecules under ambient temperature and pressure. A crucial aspect of structure reconstruction involves determining the relative orientations of each diffraction pattern and recovering the missing phase information. In this paper, we introduce a predicted model-aided algorithm for orientation determination and phase retrieval, which has been tested on various simulated datasets and has shown significant improvements in the success rate, accuracy and efficiency of XFEL data reconstruction.

Ultrafast x-ray scattering and electronic coherence at avoided crossings: complete isotropic signals

Nonadiabatic transitions at conical intersections and avoided crossings play a pivotal role in shaping the outcomes of photochemical reactions. Using the photodissociation of LiF as a model, this theoretical study explores the application of gas phase nonresonant ultrafast x-ray scattering to map nonadiabatic transitions at an avoided crossing, utilizing the part of the scattering signal that probes electronic coherence directly. The presented scattering signals are rotationally averaged and calculated from two- rather than one-electron (transition) densities, which inherently accounts for all possible electronic transitions driven by the x-ray photon. This approach provides quantitative predictions of the experimental signals, thereby facilitating future experimental endeavors to observe nonadiabatic effects and coherent electron dynamics with ultrafast x-ray scattering.

First-Order Rhombohedral-to-Cubic Phase Transition in Photoexcited GeTe.

Photoexcited GeTe undergoes a nonthermal phase transition from a rhombohedral to a rocksalt crystalline phase. The microscopic mechanism and the nature of the transition are unclear. By using constrained density functional perturbation theory and by accounting for quantum anharmonicity within the stochastic self-consistent harmonic approximation, we show that the nonthermal phase transition is strongly first order and does not involve phonon softening, at odds with the thermal one. The transition is driven by the closure of the single particle gap in the photoexcited rhombohedral phase. Finally, we show that ultrafast x-ray diffraction data are consistent with a coexistence of the two phases, as expected in a first order transition. Our results are relevant for the understanding of phase transitions and bonding in phase change materials.

Investigating binary granular mixing in a rotating drum using ultrafast X-ray computed tomography

The transient mixing dynamics of an initially segregated binary granular system in a half-filled rotating drum are experimentally investigated. The granular system consists of spherical beads having identical size. The density ratio between the two granular phases is 2.8. With its ability to scan three-dimensional opaque systems with a high frequency, the ultrafast X-ray computed tomography is used to capture the transient and steady-state segregation dynamics in the bulk. The segregation dynamics are also compared to those at the circular end-wall caps, which have been captured with a camera. The results show an axial migration of the denser particles towards the bulk and, more importantly, second-order overshooting dynamics in the radial mixing index, which tend to increase with the Froude number. The results will find application in industrial systems, where rapid mixing occurs. We also believe the presented data can serve as validation for future three-dimensional simulations focusing on the transient formation of segregation patterns in the bulk.

The high power laser facility at beamline ID24-ED at the ESRF

ABSTRACT This paper describes technical details and new scientific opportunities offered by the new High Power Laser Facility at the ESRF, opened to users since 2022. This facility enables laser-induced dynamic compression experiments probed by ultra-fast X-ray Absorption Spectroscopy at beamline ID24-ED. This capability allows to reach and probe more extreme pressure and temperature states and higher strain rates with respect to static compression, addressing open questions in fundamental, planetary and material science.

Progressive Weakening of Granite by Piezoelectric Excitation of Quartz with Alternating Current

A promising solution to reduce energy usage and mitigate the wear of drilling and comminution tools during mining operations involves inducing vibrations within the piezoelectric phases dispersed in the structure of rocks using alternating current (AC). This paper presents experimental evidence of AC-induced weakening of Kuru granite, manifested as improvements in rock drillability and reductions of strength. Sievers’ J-miniature drill tests were used to assess surface drillability. The impact of AC treatment on the quasi-static strength of granite was assessed via three-point bending and indirect tension Brazilian disk tests. The influence of AC treatment on the dynamic tensile strength of the rock was determined using split Hopkinson bar tests, with the fragmentation process captured using in situ ultra-fast synchrotron X-ray phase contrast imaging. The quasi-static tests revealed no reduction in rock strength after the AC treatment. In contrast, reductions of 25% in hardness and 18% in dynamic tensile strength were observed. Fragmentation patterns differed between treated and non-treated rocks, with treated specimens exhibiting reduced macrocrack formation during loading.

Characterization of Deformational Isomerization Potential and Interconversion Dynamics with Ultrafast X-ray Solution Scattering.

Dimeric complexes composed of d8 square planar metal centers and rigid bridging ligands provide model systems to understand the interplay between attractive dispersion forces and steric strain in order to assist the development of reliable methods to model metal dimer complexes more broadly. [Ir2 (dimen)4]2+ (dimen = para-diisocyanomenthane) presents a unique case study for such phenomena, as distortions of the optimal structure of a ligand with limited conformational flexibility counteract the attractive dispersive forces from the metal and ligand to yield a complex with two ground state deformational isomers. Here, we use ultrafast X-ray solution scattering (XSS) and optical transient absorption spectroscopy (OTAS) to reveal the nature of the equilibrium distribution and the exchange rate between the deformational isomers. The two ground state isomers have spectrally distinct electronic excitations that enable the selective excitation of one isomer or the other using a femtosecond duration pulse of visible light. We then track the dynamics of the nonequilibrium depletion of the electronic ground state population─often termed the ground state hole─with ultrafast XSS and OTAS, revealing a restoration of the ground state equilibrium in 2.3 ps. This combined experimental and theoretical study provides a critical test of various density functional approximations in the description of bridged d8-d8 metal complexes. The results show that density functional theory calculations can reproduce the primary experimental observations if dispersion interactions are added, and a hybrid functional, which includes exact exchange, is used.

Ultra-fast in vivo directional dark-field x-ray imaging for visualising magnetic control of particles for airway gene delivery

Objective. Magnetic nanoparticles can be used as a targeted delivery vehicle for genetic therapies. Understanding how they can be manipulated within the complex environment of live airways is key to their application to cystic fibrosis and other respiratory diseases. Approach. Dark-field x-ray imaging provides sensitivity to scattering information, and allows the presence of structures smaller than the detector pixel size to be detected. In this study, ultra-fast directional dark-field synchrotron x-ray imaging was utlilised to understand how magnetic nanoparticles move within a live, anaesthetised, rat airway under the influence of static and moving magnetic fields. Main results. Magnetic nanoparticles emerging from an indwelling tracheal cannula were detectable during delivery, with dark-field imaging increasing the signal-to-noise ratio of this event by 3.5 times compared to the x-ray transmission signal. Particle movement as well as particle retention was evident. Dynamic magnetic fields could manipulate the magnetic particles in situ. Significance. This is the first evidence of the effectiveness of in vivo dark-field imaging operating at these spatial and temporal resolutions, used to detect magnetic nanoparticles. These findings provide the basis for further development toward the effective use of magnetic nanoparticles, and advance their potential as an effective delivery vehicle for genetic agents in the airways of live organisms.

Deciphering Charge Transfer Processes in Transition Metal Complexes from the Perspective of Ultrafast Electronic and Nuclear Motions.

Chemical transformations in charge transfer states result from the interplay between electronic dynamics and nuclear reorganization along excited-state trajectories. Here, we investigate the ultrafast structural dynamics following photoinduced electron transfer from the metal-metal-to-ligand charge transfer state of an electron donor, a Pt dimer complex, to a covalently linked electron acceptor group using ultrafast time-resolved wide-angle X-ray scattering and optical transient absorption spectroscopy methods to disentangle the interdependence of the excited-state electronic and nuclear dynamics. Following photoexcitation, Pt-Pt bond formation and contraction takes up to 1 ps, much slower than the corresponding process in analogous complexes without electron acceptor groups. Because the Pt-Pt distance change is slow with respect to excited-state electron transfer, it can affect the rate of electron transfer. These results have potential impacts on controlling electron transfer rates via structural alterations to the electron donor group, tuning the charge transfer driving force.

Computational study of diffraction image formation from XFEL irradiated single ribosome molecule

Single particle imaging at atomic resolution is perhaps one of the most desired goals for ultrafast X-ray science with X-ray free-electron lasers. Such a capability would create great opportunity within the biological sciences, as high-resolution structural information of biosamples that may not crystallize is essential for many research areas therein. In this paper, we report on a comprehensive computational study of diffraction image formation during single particle imaging of a macromolecule, containing over one hundred thousand non-hydrogen atoms. For this study, we use a dedicated simulation framework, SIMEX, available at the European XFEL facility. Our results demonstrate the full feasibility of computational single-particle imaging studies for biological samples of realistic size. This finding is important as it shows that the SIMEX platform can be used for simulations to inform relevant single-particle-imaging experiments and help to establish optimal parameters for these experiments. This will enable more focused and more efficient single-particle-imaging experiments at XFEL facilities, making the best use of the resource-intensive XFEL operation.

Simplified Beam Hardening Correction for Ultrafast X-ray CT Imaging of Binary Granular Mixtures.

Ultrafast X-ray computed tomography is an advanced imaging technique for multiphase flows. It has been used with great success for studying gas-liquid as well as gas-solid flows. Here, we apply this technique to analyze density-driven particle segregation in a rotating drum as an exemplary use case for analyzing industrial particle mixing systems. As glass particles are used as the denser of two granular species to be mixed, beam hardening artefacts occur and hamper the data analysis. In the general case of a distribution of arbitrary materials, the inverse problem of image reconstruction with energy-dependent attenuation is often ill-posed. Consequently, commonly known beam hardening correction algorithms are often quite complex. In our case, however, the number of materials is limited. We therefore propose a correction algorithm simplified by taking advantage of the known material properties, and demonstrate its ability to improve image quality and subsequent analyses significantly.

Excited-State Identification of a Nickel-Bipyridine Photocatalyst by Time-Resolved X-ray Absorption Spectroscopy.

Photoassisted catalysis using Ni complexes is an emerging field for cross-coupling reactions in organic synthesis. However, the mechanism by which light enables and enhances the reactivity of these complexes often remains elusive. Although optical techniques have been widely used to study the ground and excited states of photocatalysts, they lack the specificity to interrogate the electronic and structural changes at specific atoms. Herein, we report metal-specific studies using transient Ni L- and K-edge X-ray absorption spectroscopy of a prototypical Ni photocatalyst, (dtbbpy)Ni(o-tol)Cl (dtb = 4,4'-di-tert-butyl, bpy = bipyridine, o-tol = ortho-tolyl), in solution. We unambiguously confirm via direct experimental evidence that the long-lived (∼5 ns) excited state is a tetrahedral metal-centered triplet state. These results demonstrate the power of ultrafast X-ray spectroscopies to unambiguously elucidate the nature of excited states in important transition-metal-based photocatalytic systems.

Speed limits of the laser-induced phase transition in FeRh

We use ultrafast x-ray diffraction and the polar time-resolved magneto-optical Kerr effect to study the laser-induced metamagnetic phase transition in two FeRh films with thicknesses below and above the optical penetration depth. In the thin film, we identify an intrinsic timescale for the light-induced nucleation of ferromagnetic (FM) domains in the antiferromagnetic material of 8ps, which is substantially longer than the time it takes for strain waves to traverse the film. For the inhomogeneously excited thicker film, only the optically excited near-surface part transforms within 8ps. For strong excitations, we observe an additional slow rise of the FM phase, which we experimentally relate to a growth of the FM phase into the depth of the layer by comparing the transient magnetization in frontside and backside excitation geometry. In the lower lying parts of the film, which are only excited via near-equilibrium heat transport, the FM phase emerges significantly slower than 8ps after heating above the transition temperature.

Deciphering Photoinduced Catalytic Reaction Mechanisms in Natural and Artificial Photosynthetic Systems on Multiple Temporal and Spatial Scales Using X-ray Probes.

Utilization of renewable energies for catalytically generating value-added chemicals is highly desirable in this era of rising energy demands and climate change impacts. Artificial photosynthetic systems or photocatalysts utilize light to convert abundant CO2, H2O, and O2 to fuels, such as carbohydrates and hydrogen, thus converting light energy to storable chemical resources. The emergence of intense X-ray pulses from synchrotrons, ultrafast X-ray pulses from X-ray free electron lasers, and table-top laser-driven sources over the past decades opens new frontiers in deciphering photoinduced catalytic reaction mechanisms on the multiple temporal and spatial scales. Operando X-ray spectroscopic methods offer a new set of electronic transitions in probing the oxidation states, coordinating geometry, and spin states of the metal catalytic center and photosensitizers with unprecedented energy and time resolution. Operando X-ray scattering methods enable previously elusive reaction steps to be characterized on different length scales and time scales. The methodological progress and their application examples collected in this review will offer a glimpse into the accomplishments and current state in deciphering reaction mechanisms for both natural and synthetic systems. Looking forward, there are still many challenges and opportunities at the frontier of catalytic research that will require further advancement of the characterization techniques.

Chemical bond reorganization in intramolecular proton transfer revealed by ultrafast X-ray photoelectron spectroscopy

Time-resolved X-ray photoelectron spectroscopy (TR-XPS) is used in a simulation study to monitor the excited state intramolecular proton transfer between oxygen and nitrogen atoms in 2-(iminomethyl)phenol. Real-time monitoring of the chemical bond breaking and forming processes is obtained through the time evolution of excited-state chemical shifts. By employing individual atomic probes of the proton donor and acceptor atoms, we predict distinct signals with opposite chemical shifts of the donor and acceptor groups during proton transfer. Details of the ultrafast bond breaking and forming dynamics are revealed by extending the classical electron spectroscopy chemical analysis to real time. Through a comparison with simulated time-resolved photoelectron spectroscopy at the valence level, the distinct advantage of TR-XPS is demonstrated thanks to its atom specificity.

The Nanoplasmonic Purcell Effect in Ultrafast and High-Light-Yield Perovskite Scintillators.

The development of X-ray scintillators with ultrahigh light yields and ultrafast response times is a long sought-after goal. In this work, a fundamental mechanism that pushes the frontiers of ultrafast X-ray scintillator performance is theoretically predicted and experimentally demonstrated: the use of nanoscale-confined surface plasmon polariton modes to tailor the scintillator response time via the Purcell effect. By incorporating nanoplasmonic materials in scintillator devices, this work predicts over tenfold enhancement in decay rate and 38% reduction in time resolution even with only a simple planar design. The nanoplasmonic Purcell effect is experimentally demonstrated using perovskite scintillators, enhancing the light yield by over 120% to 88 ± 11 ph/keV, and the decay rate by over 60% to 2.0 ± 0.2 ns for the average decay time, and 0.7 ± 0.1 ns for the ultrafast decay component, in good agreement with the predictions of ourtheoretical framework. Proof-of-concept X-ray imaging experiments are performed using nanoplasmonic scintillators, demonstrating 182% enhancement in the modulation transfer function at four line pairs per millimeter spatial frequency. This work highlights the enormous potential of nanoplasmonics in optimizing ultrafast scintillator devices for applications including time-of-flight X-ray imaging and photon-counting computed tomography.

Stimulated X-ray emission spectroscopy.

We describe an emerging hard X-ray spectroscopy technique, stimulated X-ray emission spectroscopy (S-XES). S-XES has the potential to characterize the electronic structure of 3d transition metal complexes with spectral information currently not reachable and might lead to the development of new ultrafast X-ray sources with properties beyond the stateoftheart. S-XES has become possible with the emergence of X-ray free-electron lasers (XFELs) that provide intense femtosecond X-ray pulses that can be employed to generate a population inversion of core-hole excited states resulting in stimulated X-ray emission. We describe the instrumentation, the various types of S-XES, the potential applications, the experimental challenges, and the feasibility of applying S-XES to characterize dilute systems, including the Mn4Ca cluster in the oxygen evolving complex of photosystem II.

Structure and Ultrafast X-ray Diffraction of the Hydrated Metaphosphate.

We study the pathway of metaphosphate hydration when a metaphosphate anion is dissolved in liquid water with an explicit water model. For this purpose, we propose a sequential Monte Carlo algorithm incorporated with the ab initio quantum mechanics/molecular mechanics (QM/MM) method, which can reduce the amount of ab initio QM/MM sampling while retaining the accuracy of the simulation. We demonstrate the numerical calculation of the standard enthalpy change for the successive addition reaction PO3-·2H2O + H2O ⇌ PO3-·3H2O in the liquid phase, which helps to clarify the hydration pathway of the metaphosphate. With the obtained hydrated structure of the metaphosphate anion, we perform ab initio calculations for its relaxation dynamics upon vibrational excitation and characterize the energy transfer process in solution with simulated ultrafast X-ray diffraction signals, which can be experimentally implemented with X-ray free-electron lasers.

Controlling effective field contributions to laser-induced magnetization precession by heterostructure design

Nanoscale heterostructure design can control laser-induced heat dissipation and strain propagation, as well as their efficiency for driving magnetization precession. Here, we incorporate MgO layers into the experimental platform of metallic Pt-Cu-Ni heterostructures to block the propagation of hot electrons. We show via ultrafast x-ray diffraction the capability of our platform to control the spatio-temporal shape of the transient heat and strain. Time-resolved magneto-optical Kerr experiments with systematic tuning of the magnetization precession frequency showcase control of the magnetization dynamics in the Ni layer. Our experimental analysis highlights the role of quasi-static strain as a driver of precession when the magnetic material is rapidly heated via electrons. The effective magnetic field change originating from demagnetization partially compensates the change induced by quasi-static strain. The strain pulses can be shaped via the nanoscale heterostructure design to efficiently drive the precession, paving the way for opto-magneto-acoustic devices with low heat energy deposited in the magnetic layer.

New insights into the mechanism of ultrasonic atomization for the production of metal powders in additive manufacturing

Ultrasonic atomization is one of the promising technologies for producing metal powders for additive manufacturing, where precise control of particle size and morphology is essential. In this study, we coupled an ultrasonic transducer with a carbon fiber plate and atomized liquid droplets and films under different vibration amplitudes. Water, glycerol, and pure aluminum melt were used to study the atomization mechanism and the resulting droplet/powder characteristics, respectively. High-speed optical and ultrafast synchrotron X-ray imaging were used to study in situ the ultrasonic atomization dynamics, including pulsation and clustering of cavities inside the liquid layer/films, development of capillary waves, and formation of liquid droplets. For the first time, we observed and captured the occurrence of cavitation during the atomization of resting drops, films and impact droplets. The inertial cavitation events interfered with the capillary waves across the interphase boundary, puncturing and breaking the boundary to produce atomized mist. The in situ observation revealed the intricate dynamics of ultrasonic atomization and underscored the pivotal role of cavitation events throughout the entire atomization process. We also conducted experiments on ultrasonic atomization of liquid aluminum, producing particles of perfectly spherical shape. The particle size tended to decrease with reduced vibration amplitude Our work has demonstrated the important processing strategies on how to tailor the particle size while ensuring consistent particle shape and morphology, which is the key processing capability for producing high quality powders for additive manufacturing applications.