Time-resolved X-ray Emission Spectroscopy Research Articles

PINK: a tender X-ray beamline for X-ray emission spectroscopy.

A high-flux beamline optimized for non-resonant X-ray emission spectroscopy (XES) in the tender X-ray energy range has been constructed at the BESSY II synchrotron source. The beamline utilizes a cryogenically cooled undulator that provides X-rays over the energy range 2.1 keV to 9.5 keV. This energy range provides access to XES [and in the future X-ray absorption spectroscopy (XAS)] studies of transition metals ranging from Ti to Cu (Kα, Kβ lines) and Zr to Ag (Lα, Lβ), as well as light elements including P, S, Cl, K and Ca (Kα, Kβ). The beamline can be operated in two modes. In PINK mode, a multilayer monochromator (E/ΔE ≃ 30-80) provides a high photon flux (1014 photons s-1 at 6 keV and 300 mA ring current), allowing non-resonant XES measurements of dilute substances. This mode is currently available for general user operation. X-ray absorption near-edge structure and resonant XAS techniques will be available after the second stage of the PINK commissioning, when a high monochromatic mode (E/ΔE ≃ 10000-40000) will be facilitated by a double-crystal monochromator. At present, the beamline incorporates two von Hamos spectrometers, enabling time-resolved XES experiments with time scales down to 0.1 s and the possibility of two-color XES experiments. This paper describes the optical scheme of the PINK beamline and the endstation. The design of the two von Hamos dispersive spectrometers and sample environment are discussed here in detail. To illustrate, XES spectra of phosphorus complexes, KCl, TiO2 and Co3O4 measured using the PINK setup are presented.

Experimental capabilities for liquid jet samples at sub-MHz rates at the FXE Instrument at European XFEL.

The Femtosecond X-ray Experiments (FXE) instrument at the European X-ray Free-Electron Laser (EuXFEL) provides an optimized platform for investigations of ultrafast physical, chemical and biological processes. It operates in the energy range 4.7-20 keV accommodating flexible and versatile environments for a wide range of samples using diverse ultrafast X-ray spectroscopic, scattering and diffraction techniques. FXE is particularly suitable for experiments taking advantage of the sub-MHz repetition rates provided by the EuXFEL. In this paper a dedicated setup for studies on ultrafast biological and chemical dynamics in solution phase at sub-MHz rates at FXE is presented. Particular emphasis on the different liquid jet sample delivery options and their performance is given. Our portfolio of high-speed jets compatible with sub-MHz experiments includes cylindrical jets, gas dynamic virtual nozzles and flat jets. The capability to perform multi-color X-ray emission spectroscopy (XES) experiments is illustrated by a set of measurements using the dispersive X-ray spectrometer in von Hamos geometry. Static XES data collected using a multi-crystal scanning Johann-type spectrometer are also presented. A few examples of experimental results on ultrafast time-resolved X-ray emission spectroscopy and wide-angle X-ray scattering at sub-MHz pulse repetition rates are given.

Spectroscopic and computational analysis of the oxygen evolving complex of photosystem II

The oxygen evolving activity of the Photosystem II protein sustains the biosphere. In the final catalytic step (S3 to S0 transition, duration ∼1-2 ms) within the oxygen evolving complex, an O-O bond is formed via an intricate multielectron catalysis. Using time-resolved X-ray emission spectroscopy, a method uniquely sensitive to the electronic structure of the Mn4Ca catalytic center, we demonstrate altered electronic structure very early (∼50 μs) in this transition. Suprisingly, this rapid change is unimpeded when protein functions in a D2O buffer.

Time evolution of transient plasma states from nanowire arrays irradiated at relativistic intensities

Understanding the evolution of extreme states of matter driven by relativistic laser-plasma interactions is a fundamental problem in high-field physics. This is especially true for nanostructured targets, where hydrodynamic effects play a key role within the ultra-fast time scale of laser absorption. Nanowire array targets are of particular interest as they provide an efficient means to access the ultra-high-energy-density regime due to their increased optical absorption, and have been shown to act as very efficient x-ray emission sources. Here we present analysis of time-resolved x-ray emission spectroscopy from petawatt-irradiated Nickel nanowire arrays, used to characterise the conditions achieved when scaling the performance of nanowire targets to relativistic intensities. A full time evolution of the plasma conditions is extracted from the experimental data, and shows good agreement with the physical interaction picture developed by prior computational studies.

Origin of core-to-core x-ray emission spectroscopy sensitivity to structural dynamics.

Recently, coherent structural dynamics in the excited state of an iron photosensitizer was observed through oscillations in the intensity of Kα x-ray emission spectroscopy (XES). Understanding the origin of the unexpected sensitivity of core-to-core transitions to structural dynamics is important for further development of femtosecond time-resolved XES methods and, we believe, generally necessary for interpretation of XES signals from highly non-equilibrium structures that are ubiquitous in photophysics and photochemistry. Here, we use multiconfigurational wavefunction calculations combined with atomic theory to analyze the emission process in detail. The sensitivity of core-to-core transitions to structural dynamics is due to a shift of the minimum energy metal–ligand bond distance between 1s and 2p core-hole states. A key effect is the additional contraction of the non-bonding 3s and 3p orbitals in 1s core-hole states, which decreases electron–electron repulsion and increases overlap in the metal–ligand bonds. The effect is believed to be general and especially pronounced for systems with strong bonds. The important role of 3s and 3p orbitals is consistent with the analysis of radial charge and spin densities and can be connected to the negative chemical shift observed for many transition metal complexes. The XES sensitivity to structural dynamics can be optimized by tuning the emission energy spectrometer, with oscillations up to ±4% of the maximum intensity for the current system. The theoretical predictions can be used to design experiments that separate electronic and nuclear degrees of freedom in ultrafast excited state dynamics.

Characterization of an imploding cylindrical plasma for electron transport studies using x-ray emission spectroscopy

We report on the characterization of the conditions of an imploding cylindrical plasma by time-resolved x-ray emission spectroscopy. Knowledge about this implosion platform can be applied to studies of particle transport for inertial confinement fusion schemes or to astrophysical plasmas. A cylindrical Cl-doped CH foam within a tube of solid CH was irradiated by 36 beams (Itotal ∼ 5 × 1014 W/cm2, 1.5 ns square pulse, and Etotal ∼ 16.2 kJ) of the OMEGA-60 laser to radially compress the CH toward the axis. The analysis of the time-resolved spectra showed that the compression can be described by four distinct phases, each presenting different plasma conditions. First the ablation of the cylinder is dominant; second, the foam is heated and induces a significant jump in emission intensities; third, the temperature and density of the foam reaches a maximum; and finally, the plasma expands. Ranges for the plasma temperature were inferred with the atomic physics code SCRAM (Spectroscopic Collisional-Radiative Atomic Model) and the experimental data have been compared to hydrodynamic simulations performed with the 2D code FLASH, which showed a similar implosion dynamic over time.

200-mm segmented cylindrical figured crystal for von Hamos x-ray spectrometer.

A von Hamos Bragg crystal spectrometer at 1C beamline of Pohang Accelerator Laboratory for x-ray emission spectroscopy (XES) is described. Diced Si crystals of different orientations ([111], [110], [100], and [311]) are glued onto a planoconcave glass substrate having 250/500 mm radius of curvature. To enhance the spectrometer efficiency, the length of the crystal analyzer is kept 200 mm. The emission spectra of Cu foil and Fe foil and elastic scattering from Al foil are measured using the von Hamos geometry in which curved crystals disperse the x-rays. Spectrometer efficiency and energy resolution are measured at various x-ray photon energies. X-rays are incident at 6.54 keV, 9.00 keV, 9.205 keV, and 11.51 keV for Si(440), Si(444), Si(800), and Si(933) crystal analyzers, respectively. The cylindrical figured analyzer is placed near 80° with respect to the sample, which gives better energy resolution. The spectrometer efficiency of the Si(444) crystal analyzer increases by ∼2 times when the length of the analyzer is increased from 100 mm to 200 mm. Furthermore, to measure Fe Kα1, Kα2, and Kβ simultaneously, we made a mixed crystal analyzer in which alternative strips of Si[111] and Si[110] are glued onto one preshaped cylindrical substrate. The enhanced efficiency and simultaneous measurement of Kα and Kβ emission lines will give an edge over in situ and time-resolved x-ray emission spectroscopy studies. The information extracted with a high efficiency spectrometer from low intensity XES emission lines will be useful for the in situ elemental characterization in catalytic reactions.

Micro-focused MHz pink beam for time-resolved X-ray emission spectroscopy.

The full radiation from the first harmonic of a synchrotron undulator (between 5 and 12 keV) at the Advanced Photon Source is microfocused using a stack of beryllium compound refractive lenses onto a fast-moving liquid jet and overlapped with a high-repetition-rate optical laser. This micro-focused geometry is used to perform efficient nonresonant X-ray emission spectroscopy on transient species using a dispersive spectrometer geometry. The overall usable flux achieved on target is above 1015 photons s-1 at 8 keV, enabling photoexcited systems in the liquid phase to be tracked with time resolutions from tens of picoseconds to microseconds, and using the full emission spectrum, including the weak valence-to-core signal that is sensitive to chemically relevant electronic properties.

A versatile experimental system for tracking ultrafast chemical reactions with X-ray free-electron lasers.

An experimental system, SPINETT (SACLA Pump-probe INstrumEnt for Tracking Transient dynamics), dedicated for ultrafast pump-probe experiments using X-ray free-electron lasers has been developed. SPINETT consists of a chamber operated under 1 atm helium pressure, two Von Hamos spectrometers, and a large two-dimensional detector having a short work distance. This platform covers complementary X-ray techniques; one can perform time-resolved X-ray absorption spectroscopy, time-resolved X-ray emission spectroscopy, and time-resolved X-ray diffuse scattering. Two types of liquid injectors have been prepared for low-viscosity chemical solutions and for protein microcrystals embedded in a matrix. We performed a test experiment at SPring-8 Angstrom Compact free-electron LAser and demonstrated the capability of SPINETT to obtain the local electronic structure and geometrical information simultaneously.

DIY XES - development of an inexpensive, versatile, and easy to fabricate XES analyzer and sample delivery system.

The application of X-ray emission spectroscopy (XES) has grown substantially with the development of X-ray free electron lasers, third and fourth generation synchrotron sources and high-power benchtop sources. By providing the high X-ray flux required for XES, these sources broaden the availability and application of this method of probing electronic structure. As the number of sources increase, so does the demand for X-ray emission detection and sample delivery systems that are cost effective and customizable. Here, we present a detailed fabrication protocol for von Hamos X-ray optics and give details for a 3D-printed spectrometer design. Additionally, we outline an automated, externally triggered liquid sample delivery system that can be used to repeatedly deliver nanoliter droplets onto a plastic substrate for measurement. These systems are both low cost, efficient and easy to recreate or modify depending on the application. A low cost multiple X-ray analyzer system enables measurement of dilute samples, whereas the sample delivery limits sample loss and replaces spent sample with fresh sample in the same position. While both systems can be used in a wide range of applications, the design addresses several challenges associated specifically with time-resolved XES (TRXES). As an example application, we show results from TRXES measurements of photosystem II, a dilute, photoactive protein.

Rapid evolution of the Photosystem II electronic structure during water splitting.

Photosynthetic water oxidation is a fundamental process that sustains the biosphere. A Mn4Ca cluster embedded in the photosystem II protein environment is responsible for the production of atmospheric oxygen. Here, time-resolved x-ray emission spectroscopy (XES) was used to observe the process of oxygen formation in real time. These experiments reveal that the oxygen evolution step, initiated by three sequential laser flashes, is accompanied by rapid (within 50 μs) changes to the Mn Kβ XES spectrum. However, no oxidation of the Mn4Ca core above the all MnIV state was detected to precede O-O bond formation, and the observed changes were therefore assigned to O-O bond formation dynamics. We propose that O-O bond formation occurs prior to the transfer of the final (4th) electron from the Mn4Ca cluster to the oxidized tyrosine YZ residue. This model resolves the kinetic limitations associated with O-O bond formation, and suggests an evolutionary adaptation to avoid releasing of harmful peroxide species.

Energy transfer dynamics in strongly inhomogeneous hot-dense-matter systems.

Direct measurements of energy transfer across steep density and temperature gradients in a hot-dense-matter system are presented. Hot-dense-plasma conditions were generated by high-intensity laser irradiation of a thin-foil target containing a buried metal layer. Energy transfer to the layer was measured using picosecond time-resolved x-ray emission spectroscopy. The data show two x-ray flashes in time. Fully explicit, coupled particle-in-cell and collisional-radiative atomic kinetics model predictions reproduce these observations, connecting the two x-ray flashes with staged radial energy transfer within the target.

O-O Bond Formation in Photosystem II Oxygen Evolving Complex

Photosynthetic water oxidation is a fundamental process that sustains the biosphere. Light driven water oxidation is facilitated in Nature by the Oxygen Evolving Complex (OEC) - Mn4Ca cluster embedded in the photosystem II protein. During its function, the OEC cycles through five redox states termed S0-S4 after which, oxygen is evolved. Here, time-resolved x-ray emission spectroscopy (XES) was used to observe the process of oxygen formation in real time. These experiments reveal that the oxygen evolution step, initiated by three sequential laser flashes, is accompanied by rapid (within 50 μs) changes to the Mn Kβ XES spectrum. However, no oxidation of the Mn4Ca core above the all MnIV state was detected to precede O-O bond formation, and the observed changes were therefore assigned to O-O bond formation dynamics. Our mechanism proposes O-O bond formation occurs prior to the transfer of the final (4th) electron from the Mn4Ca cluster to the oxidized TyrZ. This model resolves the kinetic limitations associated with O-O bond formation, and suggests an evolutionary adaptation to avoid releasing of harmful peroxide species. Atomistic model for the S3 state reported by us [1, 2] is indistinguishable (within the resolution of XRD) from one of the recently reported by Shen and co-workers [3]. This S3-state model incorporates a MnIV=O fragment of radicaloid character and exhibits antiferromagnetic alignment with opposite spin orientations between two Mn centers and associated oxygens creating an opportunity for a low barrier to O-O bond formation. 1. Davis et al. 2015, arXiv:1506.08862 2. Jensen et al. J Phys. Chem. Letters, 2017, 8, 2584−2589. 3. Suga et al. Nature, 2017, 543(7643), 131-135.

Ultrafast Time-Resolved Hard X-Ray Emission Spectroscopy on a Tabletop

Probing electronic states on ultrafast timescales is critical for studies of chemical reactions. A tabletop method for performing time-resolved x-ray emission spectroscopy is presented and tested using a polypyridyl iron complex.

Observation of iron spin-states using tabletop x-ray emission spectroscopy and microcalorimeter sensors

X-ray emission spectroscopy (XES) is a powerful probe of the electronic and chemical state of elemental species embedded within complex compounds. X-ray sensors that combine high resolving power and high collecting efficiency are desirable for photon-starved XES experiments such as measurements of dilute, gaseous, and radiation-sensitive samples, time-resolved measurements, and in-laboratory XES. To assess whether arrays of cryogenic microcalorimeters will be useful in photon-starved XES scenarios, we demonstrate that these emerging energy-dispersive sensors can detect the spin-state of 3d electrons of iron in two different compounds, Fe2O3 and FeS2. The measurements were conducted with a picosecond pulsed laser-driven plasma as the exciting x-ray source. The use of this tabletop source suggests that time-resolved in-laboratory XES will be possible in the future. We also present simulations of and spectra that reveal the spin-state sensitivity of different combinations of sensor resolution and accumulated counts. These simulations predict that our current experimental apparatus can perform time-resolved XES measurements on some samples with a measurement time of a few 10 s of hours per time delay.

Kinetic Modeling of the X-ray-Induced Damage to a Metalloprotein

It is well-known that biological samples undergo X-ray-induced degradation. One of the fastest occurring X-ray-induced processes involves redox modifications (reduction or oxidation) of redox-active cofactors in proteins. Here we analyze room-temperature data on the photoreduction of Mn ions in the oxygen-evolving complex (OEC) of photosystem II, one of the most radiation damage-sensitive proteins and a key constituent of natural photosynthesis in plants, green algae, and cyanobacteria. Time-resolved X-ray emission spectroscopy with wavelength-dispersive detection was used to collect data on the progression of X-ray-induced damage. A kinetic model was developed to fit experimental results, and the rate constant for the reduction of OEC Mn(III) and Mn(IV) ions by solvated electrons was determined. From this model, the possible kinetics of X-ray-induced damage at a variety of experimental conditions, such as different rates of dose deposition as well as different excitation wavelengths, can be inferred. We observed a trend of increasing dosage threshold prior to the onset of X-ray-induced damage with increasing rates of dose deposition. This trend suggests that experimentation with higher rates of dose deposition is beneficial for measurements of biological samples sensitive to radiation damage, particularly at pink beam and X-ray free electron laser sources.

Spin-state studies with XES and RIXS: From static to ultrafast

We report on extending hard X-ray emission spectroscopy (XES) along with resonant inelastic X-ray scattering (RIXS) to study ultrafast phenomena in a pump-probe scheme at MHz repetition rates. The investigated systems include low-spin (LS) FeII complex compounds, where optical pulses induce a spin-state transition to their (sub)nanosecond-lived high-spin (HS) state. Time-resolved XES clearly reflects the spin-state variations with very high signal-to-noise ratio, in agreement with HS–LS difference spectra measured at thermal spin crossover, and reference HS–LS systems in static experiments, next to multiplet calculations. The 1s2p RIXS, measured at the Fe 1s pre-edge region, shows variations after laser excitation, which are consistent with the formation of the HS state. Our results demonstrate that X-ray spectroscopy experiments with overall rather weak signals, such as RIXS, can now be reliably exploited to study chemical and physical transformations on ultrafast time scales.

High Resolution Photon Counting Detection System for Advanced Inelastic X-Ray Scattering Studies

High brilliance and high spectral resolution of synchrotron sources and associated optics enable a large number of soft-X-ray spectroscopic studies such as inelastic X-ray scattering, which is becoming a technique of choice for the investigation of the electronic properties of complex materials. The resolution of the detection system in such experiments has to match the accuracy of the probe beam in order to take the full advantage of the performance of modern synchrotron sources. In this paper we describe our advanced photon counting detection system capable of simultaneously registering both position and time of individual photons with 2-dimensional spatial accuracy of < 50 mum and timing accuracy of < 130 ps FWHM. The open face, 25 mm active area detector consists of a Z-stack of microchannel plates and a cross delay line readout and has a dark count rate of only a few counts per second. The associated electronics allows event counting rates up to ~400 KHz with 10% dead time for randomly events. We present the results of our first measurements of delayed fluorescence from different materials performed at the Advanced Light Source. Time and angular resolved fluorescence measurements allowed us to separate images for the prompt elastically scattered and the delayed photons. The detector can also distinguish registration of electrons, ions or photons by variation of the potential on its input mesh. These results demonstrate the capabilities of our detection system, which is currently being integrated into an advanced time resolved X-ray emission spectroscopy system.