Intense Femtosecond X-ray Pulses Research Articles

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.

Modeling Femtosecond Reduction of Atomic Scattering Factors in X-ray-Excited Silicon with Boltzmann Kinetic Equations

In this communication, we describe the application of Boltzmann kinetic equations for modeling massive electronic excitation in a silicon nanocrystal film after its irradiation with intense femtosecond hard X-ray pulses. This analysis was inspired by an experiment recently performed at the X-ray free-electron laser facility SACLA, which measured a significant reduction in atomic scattering factors triggered by an X-ray pulse of the intensity ∼1019 W/cm2, occurring on a timescale comparable with the X-ray pulse duration (6 fs full width at half maximum). We show that a Boltzmann kinetic equation solver can accurately follow the details of the electronic excitation in silicon atoms caused by such a hard X-ray pulse, yielding predictions in very good agreement with the experimental data.

Going around the Kok cycle of the water oxidation reaction with femtosecond X-ray crystallography.

The water oxidation reaction in photosystem II (PS II) produces most of the molecular oxygen in the atmosphere, which sustains life on Earth, and in this process releases four electrons and four protons that drive the downstream process of CO2 fixation in the photosynthetic apparatus. The catalytic center of PS II is an oxygen-bridged Mn4Ca complex (Mn4CaO5) which is progressively oxidized upon the absorption of light by the chlorophyll of the PS II reaction center, and the accumulation of four oxidative equivalents in the catalytic center results in the oxidation of two waters to dioxygen in the last step. The recent emergence of X-ray free-electron lasers (XFELs) with intense femtosecond X-ray pulses has opened up opportunities to visualize this reaction in PS II as it proceeds through the catalytic cycle. In this review, we summarize our recent studies of the catalytic reaction in PS II by following the structural changes along the reaction pathway via room-temperature X-ray crystallography using XFELs. The evolution of the electron density changes at the Mn complex reveals notable structural changes, including the insertion of OX from a new water molecule, which disappears on completion of the reaction, implicating it in the O-O bond formation reaction. We were also able to follow the structural dynamics of the protein coordinating with the catalytic complex and of channels within the protein that are important for substrate and product transport, revealing well orchestrated conformational changes in response to the electronic changes at the Mn4Ca cluster.

Picosecond to microsecond dynamics of X-ray irradiated materials at MHz pulse repetition rate

Modern X-ray free-electron lasers (XFELs) produce intense femtosecond X-ray pulses able to cause significant damage to irradiated targets. Energetic photoelectrons created upon X-ray absorption, and Auger electrons emitted after relaxation of core-hole states trigger secondary electron cascades, which contribute to the increasing transient free electron density on femtosecond timescales. Further evolution may involve energy and particle diffusion, creation of point defects, and lattice heating. This long-timescale (up to a microsecond) X-ray-induced dynamics is discussed on the example of silicon in two-dimensional geometry. For modeling, we apply an extended Two-Temperature model with electron density dynamics, nTTM, which describes relaxation of an irradiated sample between two successive X-ray pulses, emitted from XFEL at MHz pulse repetition rate. It takes into account ambipolar carrier diffusion, electronic and atomic heat conduction, as well as electron-ion coupling. To solve the nTTM system of equations in two dimensions, we developed a dedicated finite-difference integration algorithm based on Alternating Direction Implicit method with an additional predictor-corrector scheme. We show first results obtained with the model and discuss its possible applications for XFEL optics, detectors, and for diagnostics tools. In particular, the model can estimate the timescale of material relaxation relevant for beam diagnostic applications during MHz operation of contemporary and future XFELs.

Application of Boltzmann kinetic equations to model X-ray-created warm dense matter and plasma.

In this review, we describe the application of Boltzmann kinetic equations for modelling warm dense matter and plasma formed after irradiation of solid materials with intense femtosecond X-ray pulses. Classical Boltzmann kinetic equations are derived from the reduced N-particle Liouville equations. They include only single-particle densities of ions and free electrons present in the sample. The first version of the Boltzmann kinetic equation solver was completed in 2006. It could model non-equilibrium evolution of X-ray-irradiated finite-size atomic systems. In 2016, the code was adapted to study plasma created from X-ray-irradiated materials. Additional extension of the code was then also performed, enabling simulations in the hard X-ray irradiation regime. In order to avoid treatment of a very high number of active atomic configurations involved in the excitation and relaxation of X-ray-irradiated materials, an approach called 'predominant excitation and relaxation path' (PERP) was introduced. It limited the number of active atomic configurations by following the sample evolution only along most PERPs. The performance of the Boltzmann code is illustrated in the examples of X-ray-heated solid carbon and gold. Actual model limitations and further model developments are discussed. This article is part of the theme issue 'Dynamic and transient processes in warm dense matter'.

Charging and ion ejection dynamics of large helium nanodroplets exposed to intense femtosecond soft X-ray pulses

Ion ejection from charged helium nanodroplets exposed to intense femtosecond soft X-ray pulses is studied by single-pulse ion time-of-flight (TOF) spectroscopy in coincidence with small-angle X-ray scattering. Scattering images encode the droplet size and absolute photon flux incident on each droplet, while ion TOF spectra are used to determine the maximum ion kinetic energy, \(E_{\text {kin}}\), of \(\hbox {He}_{j}^{+}\) fragments (j = 1–4). Measurements span \(\hbox {He}_N\) droplet sizes between \(N\sim 10^{7}\) and \(\sim 10^{10}\) (radii \(R_0\) = 78–578 nm), and droplet charges between \(\sim 9\times 10^{-5}\) and \(\sim 3\times 10^{-3}\) e/atom. Conditions encompass a wide range of ionization and expansion regimes, from departure of all photoelectrons from the droplet, leading to pure Coulomb explosion, to substantial electron trapping by the electrostatic potential of the charged droplet, indicating the onset of hydrodynamic expansion. The unique combination of absolute X-ray intensities, droplet sizes, and ion \(E_{\text {kin}}\) on an event-by-event basis reveals a detailed picture of the correlations between the ionization conditions and the ejection dynamics of the ionic fragments. The maximum \(E_{\text {kin}}\) of He\(^{+}\) is found to be governed by Coulomb repulsion from unscreened cations across all expansion regimes. The impact of ion-atom interactions resulting from the relatively low charge densities is increasingly relevant with less electron trapping. The findings are consistent with the emergence of a charged spherical shell around a quasineutral plasma core as the degree of ionization increases. The results demonstrate a complex relationship between measured ion \(E_{\text {kin}}\) and droplet ionization conditions that can only be disentangled through the use of coincident single-pulse TOF and scattering data.

Pulse Energy and Pulse Duration Effects in the Ionization and Fragmentation of Iodomethane by Ultraintense Hard X Rays

The interaction of intense femtosecond x-ray pulses with molecules sensitively depends on the interplay between multiple photoabsorptions, Auger decay, charge rearrangement, and nuclear motion. Here, we report on a combined experimental and theoretical study of the ionization and fragmentation of iodomethane (CH_{3}I) by ultraintense (∼10^{19} W/cm^{2}) x-ray pulses at 8.3keV, demonstrating how these dynamics depend on the x-ray pulse energy and duration. We show that the timing of multiple ionization steps leading to a particular reaction product and, thus, the product's final kinetic energy, is determined by the pulse duration rather than the pulse energy or intensity. While the overall degree of ionization is mainly defined by the pulse energy, our measurement reveals that the yield of the fragments with the highest charge states is enhanced for short pulse durations, in contrast to earlier observations for atoms and small molecules in the soft x-ray domain. We attribute this effect to a decreased charge transfer efficiency at larger internuclear separations, which are reached during longer pulses.

Femtosecond laser produced periodic plasma in a colloidal crystal probed by XFEL radiation

With the rapid development of short-pulse intense laser sources, studies of matter under extreme irradiation conditions enter further unexplored regimes. In addition, an application of X-ray Free-Electron Lasers (XFELs) delivering intense femtosecond X-ray pulses, allows to investigate sample evolution in IR pump - X-ray probe experiments with an unprecedented time resolution. Here we present a detailed study of the periodic plasma created from the colloidal crystal. Both experimental data and theory modeling show that the periodicity in the sample survives to a large extent the extreme excitation and shock wave propagation inside the colloidal crystal. This feature enables probing the excited crystal, using the powerful Bragg peak analysis, in contrast to the conventional studies of dense plasma created from bulk samples for which probing with Bragg diffraction technique is not possible. X-ray diffraction measurements of excited colloidal crystals may then lead towards a better understanding of matter phase transitions under extreme irradiation conditions.

Optical second harmonic generation in LiB3O5 modulated by intense femtosecond X-ray pulses.

Many of the scientific applications for X-ray free-electron lasers seek to exploit the ultrashort pulse durations of intense X-rays to obtain femtosecond time resolution of various processes in a "pump-probe" scheme. One of the limiting factors for such experiments is the timing jitter between the X-rays and ultrashort pulses from more conventional lasers operating at near-optical wavelengths. In this work, we investigate the potential of using X-ray-induced changes in the optical second harmonic generation efficiency of a nonlinear crystal to retrieve single-shot arrival times of X-ray pulses with respect to optical laser pulses. Our experimental results and simulations show changes to the efficiency of the second harmonic generation of 12%, approximately three times larger than the measured changes in the transmission of the 800 nm center-wavelength fundamental pulse. Further experiments showing even larger changes in the transmission of 400 nm center-wavelength pulses show that the mechanism of the second harmonic generation efficiency modulation is mainly the result of X-ray-induced changes in the linear absorption coefficients near 400 nm. We demonstrate and characterize a cross-correlation tool based on this effect in reference to a previously demonstrated method of X-ray/optical cross-correlation.

Ultrafast Structural Dynamics of Nanoparticles in Intense Laser Fields.

Femtosecond laser pulses have opened new frontiers for the study of ultrafast phase transitions and nonequilibrium states of matter. In this Letter, we report on structural dynamics in atomic clusters pumped with intense near-infrared (NIR) pulses into a nanoplasma state. Employing wide-angle scattering with intense femtosecond x-ray pulses from a free-electron laser source, we find that highly excited xenon nanoparticles retain their crystalline bulk structure and density in the inner core long after the driving NIR pulse. The observed emergence of structural disorder in the nanoplasma is consistent with a propagation from the surface to the inner core of the clusters.

Charge transfer in dissociating iodomethane and fluoromethane molecules ionized by intense femtosecond X-ray pulses.

Ultrafast electron transfer in dissociating iodomethane and fluoromethane molecules was studied at the Linac Coherent Light Source free-electron laser using an ultraviolet-pump, X-ray-probe scheme. The results for both molecules are discussed with respect to the nature of their UV excitation and different chemical properties. Signatures of long-distance intramolecular charge transfer are observed for both species, and a quantitative analysis of its distance dependence in iodomethane is carried out for charge states up to I21+. The reconstructed critical distances for electron transfer are in good agreement with a classical over-the-barrier model and with an earlier experiment employing a near-infrared pump pulse.

Facilitating model reconstruction for single-particle scattering using small-angle X-ray scattering methods.

X-ray free-electron lasers generate intense femtosecond X-ray pulses, so that high-resolution structure determination becomes feasible from noncrystalline samples, such as single particles or single molecules. At the moment, the orientation of sample particles cannot be precisely controlled, and consequently the unknown orientation needs to be recovered using computational algorithms. This delays the model reconstruction until all the scattering patterns have been re-oriented, which often entails a long elapse of time and until the completion of the experiment. The scattering patterns from single particles or multiple particles can be summed to form a virtual powder diffraction pattern, and the low-resolution region, corresponding to the small-angle X-ray scattering (SAXS) regime, can be analysed using existing SAXS methods. This work presents a pipeline that converts single-particle data sets into SAXS data, from which real-time model reconstruction is achieved using the model retrieval approach implemented in the software package SASTBX [Liu, Hexemer & Zwart (2012). J. Appl. Cryst.45, 587-593]. To illustrate the applications, two case studies are presented with real experimental data sets collected at the Linac Coherent Light Source.

Towards characterization of photo-excited electron transfer and catalysis in natural and artificial systems using XFELs.

The ultra-bright femtosecond X-ray pulses provided by X-ray Free Electron Lasers (XFELs) open capabilities for studying the structure and dynamics of a wide variety of biological and inorganic systems beyond what is possible at synchrotron sources. Although the structure and chemistry at the catalytic sites have been studied intensively in both biological and inorganic systems, a full understanding of the atomic-scale chemistry requires new approaches beyond the steady state X-ray crystallography and X-ray spectroscopy at cryogenic temperatures. Following the dynamic changes in the geometric and electronic structure at ambient conditions, while overcoming X-ray damage to the redox active catalytic center, is key for deriving reaction mechanisms. Such studies become possible by using the intense and ultra-short femtosecond X-ray pulses from an XFEL, where sample is probed before it is damaged. We have developed methodology for simultaneously collecting X-ray diffraction data and X-ray emission spectra, using an energy dispersive spectrometer, at ambient conditions, and used this approach to study the room temperature structure and intermediate states of the photosynthetic water oxidizing metallo-protein, photosystem II. Moreover, we have also used this setup to simultaneously collect the X-ray emission spectra from multiple metals to follow the ultrafast dynamics of light-induced charge transfer between multiple metal sites. A Mn-Ti containing system was studied at an XFEL to demonstrate the efficacy and potential of this method.

Femtosecond x-ray induced fragmentation of Ho3N@C80

SynopsisWe report on new data regarding on the photoionization and fragmentation dynamics of gas phase endohedral fullerenes Ho3N@C80 obtained with intense femtosecond X-ray pulses from the Linac Coherent Light Source (LCLS) free electron laser (FEL).

Time-resolved studies with FELs

Intense femtosecond VUV, XUV, and X-ray pulses from free-electron lasers (FELs) enable time-resolved experiments studying ultrafast dynamics in a large variety of systems relevant, e.g., to physics, chemistry, biology, and material sciences. In this paper, we focus on time-resolved studies of gas-phase molecules, which lie at the crossroad between atomic, molecular and optical physics and ultrafast photochemistry. We describe the current status of the field and discuss typical experimental configurations used for pump-probe experiments with FELs. We illustrate them with three recent examples for such experiments performed at the FLASH and LCLS FELs studying charge transfer following XUV and X-ray photoabsorption as well as photoelectron diffraction from aligned molecules. We conclude with a short outlook on future developments and perspectives for femtosecond pump-probe experiments with FELs.

The linac coherent light source single particle imaging road map.

Intense femtosecond x-ray pulses from free-electron laser sources allow the imaging of individual particles in a single shot. Early experiments at the Linac Coherent Light Source (LCLS) have led to rapid progress in the field and, so far, coherent diffractive images have been recorded from biological specimens, aerosols, and quantum systems with a few-tens-of-nanometers resolution. In March 2014, LCLS held a workshop to discuss the scientific and technical challenges for reaching the ultimate goal of atomic resolution with single-shot coherent diffractive imaging. This paper summarizes the workshop findings and presents the roadmap toward reaching atomic resolution, 3D imaging at free-electron laser sources.

Serial femtosecond crystallography: the first five years.

Protein crystallography using synchrotron radiation sources has had a tremendous impact on biology, having yielded the structures of thousands of proteins and given detailed insight into their mechanisms. However, the technique is limited by the requirement for macroscopic crystals, which can be difficult to obtain, as well as by the often severe radiation damage caused in diffraction experiments, in particular when using tiny crystals. To slow radiation damage, data collection is typically performed at cryogenic temperatures. With the advent of free-electron lasers (FELs) capable of delivering extremely intense femtosecond X-ray pulses, this situation appears to be remedied, allowing the structure determination of undamaged macromolecules using either macroscopic or microscopic crystals. The latter are exposed to the FEL beam in random orientations and their diffraction data are collected at cryogenic or room temperature in a serial fashion, since each crystal is destroyed upon a single exposure. The new approaches required for crystal growth and delivery, and for diffraction data analysis, including de novo phasing, are reviewed. The opportunities and challenges of SFX are described, including applications such as time-resolved measurements and the analysis of radiation damage-prone systems.

Generation and structure of extremely large clusters in pulsed jets.

Extremely large xenon clusters with sizes exceeding the predictions of the Hagena scaling law by several orders of magnitude are shown to be produced in pulsed gas jets. The cluster sizes are determined using single-shot single-particle imaging experiments with short-wavelength light pulses from the free-electron laser in Hamburg (FLASH). Scanning the time delay between the pulsed cluster source and the intense femtosecond x-ray pulses first shows a main plateau with size distributions in line with the scaling laws, which is followed by an after-pulse of giant clusters. For the extremely large clusters with radii of several hundred nanometers the x-ray scattering patterns indicate a grainy substructure of the particles, suggesting that they grow by cluster coagulation.

Diffraction before destruction.

X-ray free-electron lasers have opened up the possibility of structure determination of protein crystals at room temperature, free of radiation damage. The femtosecond-duration pulses of these sources enable diffraction signals to be collected from samples at doses of 1000 MGy or higher. The sample is vaporized by the intense pulse, but not before the scattering that gives rise to the diffraction pattern takes place. Consequently, only a single flash diffraction pattern can be recorded from a crystal, giving rise to the method of serial crystallography where tens of thousands of patterns are collected from individual crystals that flow across the beam and the patterns are indexed and aggregated into a set of structure factors. The high-dose tolerance and the many-crystal averaging approach allow data to be collected from much smaller crystals than have been examined at synchrotron radiation facilities, even from radiation-sensitive samples. Here, we review the interaction of intense femtosecond X-ray pulses with materials and discuss the implications for structure determination. We identify various dose regimes and conclude that the strongest achievable signals for a given sample are attained at the highest possible dose rates, from highest possible pulse intensities.

Multiphoton ionization and fragmentation of molecules with the LCLS X-ray FEL

The photoionization of diatomic and polyatomic molecules with intense femtosecond X-ray pulses from the Linac Coherent Light Source free electron laser have been investigated using photoion spectrometry. The dominant mechanism measured is multiple core-ionization-Auger decay cycles leading to molecular fragmentation followed by the production of highly charged atomic ions. This work sheds light on fundamental aspects of matter–intense X-ray interaction and impacts research relevant to matter under extreme conditions and molecular radiation damage, pertinent to single bio-molecule imaging.