(Sub-)Picosecond Surface Correlations of Femtosecond Laser Excited Al-Coated Multilayers Observed by Grazing-Incidence X-ray Scattering.

Femtosecond high-intensity laser pulses at intensities surpassing 1014 W/cm2 can generate a diverse range of functional surface nanostructures. Achieving precise control over the production of these functional structures necessitates a thorough understanding of the surface morphology dynamics with nanometer-scale spatial resolution and picosecond-scale temporal resolution. In this study, we show that single XFEL pulses can elucidate structural changes on surfaces induced by laser-generated plasmas using grazing-incidence small-angle X-ray scattering (GISAXS). Using aluminium-coated multilayer samples we distinguish between sub-picosecond (ps) surface morphology dynamics and subsequent multi-ps subsurface density dynamics with nanometer-depth sensitivity. The observed subsurface density dynamics serve to validate advanced simulation models representing matter under extreme conditions. Our findings promise to open new avenues for laser material-nanoprocessing and high-energy-density science.

Disentangling the evolution of electrons and holes in photoexcited ZnO nanoparticles.

The evolution of charge carriers in photoexcited room temperature ZnO nanoparticles in solution is investigated using ultrafast ultraviolet photoluminescence spectroscopy, ultrafast Zn K-edge absorption spectroscopy, and ab initio molecular dynamics (MD) simulations. The photoluminescence is excited at 4.66 eV, well above the band edge, and shows that electron cooling in the conduction band and exciton formation occur in <500 fs, in excellent agreement with theoretical predictions. The x-ray absorption measurements, obtained upon excitation close to the band edge at 3.49 eV, are sensitive to the migration and trapping of holes. They reveal that the 2 ps transient largely reproduces the previously reported transient obtained at 100 ps time delay in synchrotron studies. In addition, the x-ray absorption signal is found to rise in ∼1.4 ps, which we attribute to the diffusion of holes through the lattice prior to their trapping at singly charged oxygen vacancies. Indeed, the MD simulations show that impulsive trapping of holes induces an ultrafast expansion of the cage of Zn atoms in <200 fs, followed by an oscillatory response at a frequency of ∼100 cm-1, which corresponds to a phonon mode of the system involving the Zn sub-lattice.

Transonic dislocation propagation in diamond.

The motion of line defects (dislocations) has been studied for more than 60 years, but the maximum speed at which they can move is unresolved. Recent models and atomistic simulations predict the existence of a limiting velocity of dislocation motion between the transonic and subsonic ranges at which the self-energy of dislocation diverges, though they do not deny the possibility of the transonic dislocations. We used femtosecond x-ray radiography to track ultrafast dislocation motion in shock-compressed single-crystal diamond. By visualizing stacking faults extending faster than the slowest sound wave speed of diamond, we show the evidence of partial dislocations at their leading edge moving transonically. Understanding the upper limit of dislocation mobility in crystals is essential to accurately model, predict, and control the mechanical properties of materials under extreme conditions.

Experimental Demonstration to Control the Pulse Length of Coherent Undulator Radiation by Chirped Microbunching.

In seeded free electron lasers (FELs), the temporal profile of FEL pulses usually reflects that of the seed pulse, and, thus, shorter FEL pulses are available with shorter seed pulses. In an extreme condition, however, this correlation is violated; the FEL pulse is stretched by the so-called slippage effect in undulators, when the seed pulse is ultimately short, e.g., few-cycles long. In a previous Letter, we have proposed a scheme to suppress the slippage effect and reduce the pulse length of FELs ultimately down to a single-cycle duration, which is based on "chirped microbunching," or an electron density modulation with a varying modulation period. Toward realization of FELs based on the proposed scheme, experiments have been carried out to demonstrate its fundamental mechanism in the NewSUBARU synchrotron radiation facility, using an ultrashort seed pulse with the pulse length shorter than five cycles. Experimental results of spectral and cross-correlation measurements have been found to be in reasonable agreement with the theoretical predictions, which strongly suggests the successful demonstration of the proposed scheme.

Ultrafast X-Ray Scattering Reveals Composite Amplitude Collective Mode in the Weyl Charge Density Wave Material (TaSe_{4})_{2}I.

We report ultrafast x-ray scattering experiments of the quasi-1D charge density wave (CDW) material (TaSe_{4})_{2}I following ultrafast infrared photoexcitation. From the time-dependent diffraction signal at the CDW sidebands we identify a 0.11 THz amplitude mode derived primarily from a transverse acoustic mode of the high-symmetry structure. From our measurements we determine that this mode interacts with the valence charge indirectly through another collective mode, and that the CDW system in (TaSe_{4})_{2}I has a composite nature supporting multiple dynamically active structural degrees of freedom.

X-ray free electron laser observation of ultrafast lattice behaviour under femtosecond laser-driven shock compression in iron.

Over the past century, understanding the nature of shock compression of condensed matter has been a major topic. About 20 years ago, a femtosecond laser emerged as a new shock-driver. Unlike conventional shock waves, a femtosecond laser-driven shock wave creates unique microstructures in materials. Therefore, the properties of this shock wave may be different from those of conventional shock waves. However, the lattice behaviour under femtosecond laser-driven shock compression has never been elucidated. Here we report the ultrafast lattice behaviour in iron shocked by direct irradiation of a femtosecond laser pulse, diagnosed using X-ray free electron laser diffraction. We found that the initial compression state caused by the femtosecond laser-driven shock wave is the same as that caused by conventional shock waves. We also found, for the first time experimentally, the temporal deviation of peaks of stress and strain waves predicted theoretically. Furthermore, the existence of a plastic wave peak between the stress and strain wave peaks is a new finding that has not been predicted even theoretically. Our findings will open up new avenues for designing novel materials that combine strength and toughness in a trade-off relationship.

Diamond formation kinetics in shock-compressed C─H─O samples recorded by small-angle x-ray scattering and x-ray diffraction.

Extreme conditions inside ice giants such as Uranus and Neptune can result in peculiar chemistry and structural transitions, e.g., the precipitation of diamonds or superionic water, as so far experimentally observed only for pure C─H and H2O systems, respectively. Here, we investigate a stoichiometric mixture of C and H2O by shock-compressing polyethylene terephthalate (PET) plastics and performing in situ x-ray probing. We observe diamond formation at pressures between 72 ± 7 and 125 ± 13 GPa at temperatures ranging from ~3500 to ~6000 K. Combining x-ray diffraction and small-angle x-ray scattering, we access the kinetics of this exotic reaction. The observed demixing of C and H2O suggests that diamond precipitation inside the ice giants is enhanced by oxygen, which can lead to isolated water and thus the formation of superionic structures relevant to the planets' magnetic fields. Moreover, our measurements indicate a way of producing nanodiamonds by simple laser-driven shock compression of cheap PET plastics.

Determination of sub-ps lattice dynamics in FeRh thin films.

Understanding the ultrashort time scale structural dynamics of the FeRh metamagnetic phase transition is a key element in developing a complete explanation of the mechanism driving the evolution from an antiferromagnetic to ferromagnetic state. Using an X-ray free electron laser we determine, with sub-ps time resolution, the time evolution of the (-101) lattice diffraction peak following excitation using a 35 fs laser pulse. The dynamics at higher laser fluence indicates the existence of a transient lattice state distinct from the high temperature ferromagnetic phase. By extracting the lattice temperature and comparing it with values obtained in a quasi-static diffraction measurement, we estimate the electron-phonon coupling in FeRh thin films as a function of laser excitation fluence. A model is presented which demonstrates that the transient state is paramagnetic and can be reached by a subset of the phonon bands. A complete description of the FeRh structural dynamics requires consideration of coupling strength variation across the phonon frequencies.

Crystallization kinetics of atomic crystals revealed by a single-shot and single-particle X-ray diffraction experiment.

Crystallization is a fundamental natural phenomenon and the ubiquitous physical process in materials science for the design of new materials. So far, experimental observations of the structural dynamics in crystallization have been mostly restricted to slow dynamics. We present here an exclusive way to explore the dynamics of crystallization in highly controlled conditions (i.e., in the absence of impurities acting as seeds of the crystallites) as it occurs in vacuum. We have measured the early formation stage of solid Xe nanoparticles nucleated in an expanding supercooled Xe jet by means of an X-ray diffraction experiment with 10-fs X-ray free-electron laser (XFEL) pulses. We found that the structure of Xe nanoparticles is not pure face-centered cubic (fcc), the expected stable phase, but a mixture of fcc and randomly stacked hexagonal close-packed (rhcp) structures. Furthermore, we identified the instantaneous coexistence of the comparably sized fcc and rhcp domains in single Xe nanoparticles. The observations are explained by the scenario of structural aging, in which the nanoparticles initially crystallize in the highly stacking-disordered rhcp phase and the structure later forms the stable fcc phase. The results are reminiscent of analogous observations in hard-sphere systems, indicating the universal role of the stacking-disordered phase in nucleation.

Spatially resolved single-shot absorption spectroscopy with x-ray free electron laser pulse.

A new method of spatially resolved single-shot absorption spectroscopy for an x-ray free electron laser (XFEL) pulse has been developed by using a dispersive spectrometer and an elliptical mirror to enhance the spatial resolution. As a demonstration, we performed x-ray absorption near-edge structure measurement of Cu with a pump-probe scheme combining an XFEL pulse and a high-power femtosecond laser pulse. In the experiment, changes of an absorption spectrum in a plasma generated with a laser shot were successfully observed. The method will be a powerful tool for experiments requiring a spatial resolution and/or a single-shot measurement, such as high energy density science using a high-power laser pulse.

Ultrafast olivine-ringwoodite transformation during shock compression.

Meteorites from interplanetary space often include high-pressure polymorphs of their constituent minerals, which provide records of past hypervelocity collisions. These collisions were expected to occur between kilometre-sized asteroids, generating transient high-pressure states lasting for several seconds to facilitate mineral transformations across the relevant phase boundaries. However, their mechanisms in such a short timescale were never experimentally evaluated and remained speculative. Here, we show a nanosecond transformation mechanism yielding ringwoodite, which is the most typical high-pressure mineral in meteorites. An olivine crystal was shock-compressed by a focused high-power laser pulse, and the transformation was time-resolved by femtosecond diffractometry using an X-ray free electron laser. Our results show the formation of ringwoodite through a faster, diffusionless process, suggesting that ringwoodite can form from collisions between much smaller bodies, such as metre to submetre-sized asteroids, at common relative velocities. Even nominally unshocked meteorites could therefore contain signatures of high-pressure states from past collisions.

Femtosecond Charge Density Modulations in Photoexcited CuWO4.

Copper tungstate (CuWO4) is an important semiconductor with a sophisticated and debatable electronic structure that has a direct impact on its chemistry. Using the PAL-XFEL source, we study the electronic dynamics of photoexcited CuWO4. The Cu L3 X-ray absorption spectrum shifts to lower energy upon photoexcitation, which implies that the photoexcitation process from the oxygen valence band to the tungsten conduction band effectively increases the charge density on the Cu atoms. The decay time of this spectral change is 400 fs indicating that the increased charge density exists only for a very short time and relaxes electronically. The initial increased charge density gives rise to a structural change on a time scale longer than 200 ps.

Tunable vacuum ultraviolet cross-luminescence from KMgF under high pressure as potential fast-response scintillator.

We report on the potential of the potassium magnesium fluoride (KMgF) crystal as a fast-response scintillator with tunable cross-luminescence (CL) emission wavelength through high-pressure applications. By performing first-principles density functional theory calculations using the Perdew-Burke-Ernzerhof (PBE) hybrid functional including exact exchange (PBE0) and Green's function and screened Coulomb interaction approximation as implemented in the Vienna Ab initio Simulation Package using plane-wave basis sets within the projector-augmented wave method, we identify the specific valence-to-core band transition that results in the experimentally observed CL emission at 148 nm (8.38 eV) and 170 nm (7.29 eV) wavelengths with intrinsically fast decay times of 290 ps and 210 ps, respectively. Uniform volume compression through hydrostatic high-pressure applications could decrease the energy gap between the valence and core bands, potentially shifting the CL emission wavelength to the ultraviolet (UV) region from 200 nm (6.2 eV) to 300 nm (4.1 eV). The ability to tune and shift the CL emission to UV wavelengths allows for the detection of the CL emission using UV-sensitive photodetectors in ambient atmosphere instead of highly specialized vacuum UV detectors operating in vacuum while maintaining the intrinsically fast CL decay times, thereby opening up new possibilities for KMgF as a fast-response scintillator.

Development of an undulator with a variable magnetic field profile.

An undulator generating a magnetic field whose longitudinal profile is arbitrarily varied has been developed, which is one of the key components in a number of proposed new concepts in free-electron lasers. The undulator is composed of magnet modules, each of which corresponds to a single undulator period, and is driven by a linear actuator to change the magnetic gap independently. To relax the requirement on the actuator, the mechanical load on each module due to magnetic force acting from opponent and adjacent modules is reduced by means of two kinds of spring systems. The performance of the constructed undulator has been successfully demonstrated by magnetic measurement and characterization of synchrotron radiation.

Mapping the emergence of molecular vibrations mediating bond formation.

Fundamental studies of chemical reactions often consider the molecular dynamics along a reaction coordinate using a calculated or suggested potential energy surface1-5. But fully mapping such dynamics experimentally, by following all nuclear motions in a time-resolved manner-that is, the motions of wavepackets-is challenging and has not yet been realized even for the simple stereotypical bimolecular reaction6-8: A-B + C â†’ A + B-C. Here we track the trajectories of these vibrational wavepackets during photoinduced bond formation of the gold trimer complex [Au(CN)2-]3 in an aqueous monomer solution, using femtosecond X-ray liquidography9-12 with X-ray free-electron lasers13,14. In the complex, which forms when three monomers A, B and C cluster together through non-covalent interactions15,16, the distance between A and B is shorter than that between B and C. Tracking the wavepacket in three-dimensional nuclear coordinates reveals that within the first 60 femtoseconds after photoexcitation, a covalent bond forms between A and B to give A-B + C. The second covalent bond, between B and C, subsequently forms within 360 femtoseconds to give a linear and covalently bonded trimer complex A-B-C. The trimer exhibits harmonic vibrations that we map and unambiguously assign to specific normal modes using only the experimental data. In principle, more intense X-rays could visualize the motion not only of highly scattering atoms such as gold but also of lighter atoms such as carbon and nitrogen, which will open the door to the direct tracking of the atomic motions involved in many chemical reactions.

Evidence of shock-compressed stishovite above 300 GPa.

SiO2 is one of the most fundamental constituents in planetary bodies, being an essential building block of major mineral phases in the crust and mantle of terrestrial planets (1-10 ME). Silica at depths greater than 300 km may be present in the form of the rutile-type, high pressure polymorph stishovite (P42/mnm) and its thermodynamic stability is of great interest for understanding the seismic and dynamic structure of planetary interiors. Previous studies on stishovite via static and dynamic (shock) compression techniques are contradictory and the observed differences in the lattice-level response is still not clearly understood. Here, laser-induced shock compression experiments at the LCLS- and SACLA XFEL light-sources elucidate the high-pressure behavior of stishovite on the lattice-level under in situ conditions on the Hugoniot to pressures above 300 GPa. We find stishovite is still (meta-)stable at these conditions, and does not undergo any phase transitions. This contradicts static experiments showing structural transformations to the CaCl2, α-PbO2 and pyrite-type structures. However, rate-limited kinetic hindrance may explain our observations. These results are important to our understanding into the validity of EOS data from nanosecond experiments for geophysical applications.

Characterizing crystalline defects in single nanoparticles from angular correlations of single-shot diffracted X-rays.

Characterizing and controlling the uniformity of nanoparticles is crucial for their application in science and technology because crystalline defects in the nanoparticles strongly affect their unique properties. Recently, ultra-short and ultra-bright X-ray pulses provided by X-ray free-electron lasers (XFELs) opened up the possibility of structure determination of nanometre-scale matter with Å spatial resolution. However, it is often difficult to reconstruct the 3D structural information from single-shot X-ray diffraction patterns owing to the random orientation of the particles. This report proposes an analysis approach for characterizing defects in nanoparticles using wide-angle X-ray scattering (WAXS) data from free-flying single nanoparticles. The analysis method is based on the concept of correlated X-ray scattering, in which correlations of scattered X-ray are used to recover detailed structural information. WAXS experiments of xenon nanoparticles, or clusters, were conducted at an XFEL facility in Japan by using the SPring-8 Ångstrom compact free-electron laser (SACLA). Bragg spots in the recorded single-shot X-ray diffraction patterns showed clear angular correlations, which offered significant structural information on the nanoparticles. The experimental angular correlations were reproduced by numerical simulation in which kinematical theory of diffraction was combined with geometric calculations. We also explain the diffuse scattering intensity as being due to the stacking faults in the xenon clusters.

Photoswitching mechanism of a fluorescent protein revealed by time-resolved crystallography and transient absorption spectroscopy.

Reversibly switchable fluorescent proteins (RSFPs) serve as markers in advanced fluorescence imaging. Photoswitching from a non-fluorescent off-state to a fluorescent on-state involves trans-to-cis chromophore isomerization and proton transfer. Whereas excited-state events on the ps timescale have been structurally characterized, conformational changes on slower timescales remain elusive. Here we describe the off-to-on photoswitching mechanism in the RSFP rsEGFP2 by using a combination of time-resolved serial crystallography at an X-ray free-electron laser and ns-resolved pump-probe UV-visible spectroscopy. Ten ns after photoexcitation, the crystal structure features a chromophore that isomerized from trans to cis but the surrounding pocket features conformational differences compared to the final on-state. Spectroscopy identifies the chromophore in this ground-state photo-intermediate as being protonated. Deprotonation then occurs on the µs timescale and correlates with a conformational change of the conserved neighbouring histidine. Together with a previous excited-state study, our data allow establishing a detailed mechanism of off-to-on photoswitching in rsEGFP2.

Photoinduced anisotropic distortion as the electron trapping site of tungsten trioxide by ultrafast W L1-edge X-ray absorption spectroscopy with full potential multiple scattering calculations.

Understanding the excited state of photocatalysts is significant to improve their activity for water splitting reaction. X-ray absorption fine structure (XAFS) spectroscopy in X-ray free electron lasers (XFEL) is a powerful method to address dynamic changes in electronic states and structures of photocatalysts in the excited state in ultrafast short time scales. The ultrafast atomic-scale local structural change in photoexcited WO3 was observed by W L1 edge XAFS spectroscopy using an XFEL. An anisotropic local distortion around the W atom could reproduce well the spectral features at a delay time of 100 ps after photoexcitation based on full potential multiple scattering calculations. The distortion involved the movement of W to shrink the shortest W-O bonds and elongate the longest one. The movement of the W atom could be explained by the filling of the dxy and dzx orbitals, which were originally located at the bottom of the conduction band with photoexcited electrons.