Special Issue on Frontiers of Free-Electrons Laser Science Series II

The matter in extreme conditions end station at the Linac Coherent Light Source (LCLS) is a new tool enabling accurate pump–probe measurements for studying the physical properties of matter in the high-energy density (HED) physics regime. This instrument combines the world's brightest x-ray source, the LCLS x-ray beam, with high-power lasers consisting of two nanosecond Nd:glass laser beams and one short-pulse Ti:sapphire laser. These lasers produce short-lived states of matter with high pressures, high temperatures or high densities with properties that are important for applications in nuclear fusion research, laboratory astrophysics and the development of intense radiation sources. In the first experiments, we have performed highly accurate x-ray diffraction and x-ray Thomson scattering measurements on shock-compressed matter resolving the transition from compressed solid matter to a co-existence regime and into the warm dense matter state. These complex charged-particle systems are dominated by strong correlations and quantum effects. They exist in planetary interiors and laboratory experiments, e.g., during high-power laser interactions with solids or the compression phase of inertial confinement fusion implosions. Applying record peak brightness x-rays resolves the ionic interactions at atomic (Ångstrom) scale lengths and measure the static structure factor, which is a key quantity for determining equation of state data and important transport coefficients. Simultaneously, spectrally resolved measurements of plasmon features provide dynamic structure factor information that yield temperature and density with unprecedented precision at micron-scale resolution in dynamic compression experiments. These studies have demonstrated our ability to measure fundamental thermodynamic properties that determine the state of matter in the HED physics regime.

Recent technological advances in the generation of intense femtosecond pulses have made covariance mapping an attractive analytical technique. The laser pulses available are so intense that often thousands of ionisation and Coulomb explosion events will occur within each pulse. To understand the physics of these processes the photoelectrons and photoions need to be correlated, and covariance mapping is well suited for operating at the high counting rates of these laser sources. Partial covariance is particularly useful in experiments with x-ray free electron lasers, because it is capable of suppressing pulse fluctuation effects. A variety of covariance mapping methods is described: simple, partial (single- and multi-parameter), sliced, contingent and multi-dimensional. The relationship to coincidence techniques is discussed. Covariance mapping has been used in many areas of science and technology: inner-shell excitation and Auger decay, multiphoton and multielectron ionisation, time-of-flight and angle-resolved spectrometry, infrared spectroscopy, nuclear magnetic resonance imaging, stimulated Raman scattering, directional gamma ray sensing, welding diagnostics and brain connectivity studies (connectomics). This review gives practical advice for implementing the technique and interpreting the results, including its limitations and instrumental constraints. It also summarises recent theoretical studies, highlights unsolved problems and outlines a personal view on the most promising research directions.

We investigate the multi-photon process of above-threshold ionization for the light elements hydrogen, carbon, nitrogen, and oxygen in the hard x-ray regime. Numerical challenges are discussed and by comparing Hartree–Fock–Slater calculations with configuration–interaction–singles results we justify the mean-field potential approach in this regime. We present a theoretical prediction of two-photon above-threshold-ionization cross sections for the mentioned elements. Moreover, we study how the importance of above-threshold ionization varies with intensity. We find that for carbon, at x-ray intensities around ${{10}^{23}}\ {\rm W}\;{\rm c}{{{\rm m}}^{-2}}$, two-photon above-threshold ionization of the K-shell electrons is as probable as one-photon ionization of the L-shell electrons.

We report on the ionization and nanoplasma dynamics of small xenon clusters irradiated by intense, short pulses of a short-wavelength free-electron laser. Fluorescence spectroscopy indicates that inelastic electron collisions play a prominent role in the formation of the highest charge states. From the spectral distribution an electron temperature of 27 eV is deduced which corresponds to the average excess energy of the Auger- and photoelectrons ionized from individual atoms but trapped in the cluster core. This suggests that fluorescence spectra reflect a very early stage within the nanoplasma dynamics and shows how a part of the kinetic energy of the plasma electrons trapped in the cluster potential is transferred to the ions.

Electrons released from clusters through strong x-ray pulses show broad kinetic-energy spectra, extending from the atomic excess energy down to the threshold, where usually a strong peak appears. These low-energy electrons are normally attributed to evaporation from the nano-plasma formed in the highly-charged clusters. Here, it is shown that also directly emitted photo-electrons generate a pronounced spectral feature close to threshold. Furthermore, we give an analytical approximation for the direct photo-electron spectrum.

Intense pulses from a short wavelength free-electron laser turn xenon nanoparticles into a high energy density nanoplasma within femtoseconds. Recently, the generation of multiply charged xenon ions during the initial phase of plasma evolution has been studied by energy-resolved XUV fluorescence detection as a function of cluster size and cluster composition [1]. In the present contribution we give a detailed analysis of the corresponding radiative transitions after resonant excitation of the 4d electron shell at intensities of 2 × 10¹² − 2.45 × 10¹⁵ W cm⁻². The evaluation of charge-state specific fluorescence yields as a function of FEL power density demonstrates that plasma effects such as ionization potential lowering, electron impact excitation, ionization, and energy redistribution govern the laser-induced non-equilibrium dynamics in xenon clusters.

We have developed an experimental apparatus named KOTOBUKI-1 for use in the coherent x-ray diffraction imaging experiments of frozen-hydrated non-crystalline particles at cryogenic temperature. The apparatus allows us to collect diffraction data for frozen-hydrated specimens at 66 K and provides an experimental environment to easily transfer frozen-hydrated specimens from liquid nitrogen storage to the specimen stage for x-ray exposure. Since 2012, the apparatus has been used in the single-shot diffraction data collection of non-crystalline biological cells and cellular components with dimensions from micrometer to submicrometer using x-ray free electron lasers at SACLA. Here we report on the performance of the KOTOBUKI-1 diffraction apparatus and some structure analyses of biological cells and cellular components. Based on the present results, we also discuss the future developments of diffraction apparatus for more efficient data collection.

Single core-hole (SCH) and double core-hole excited state molecular dynamics (MD) calculations for neutral and cationic H₂O, NH₃, and CH₄ have been performed to examine geometry relaxation after core excitation. We observed faster X–H (X = C, N, O) bond elongation for the core-ionized state produced from the valence cationic molecule and the double-core-ionized state produced from the ground and valence cationic molecules than for the first resonant SCH state. Using the results of SCH MD simulations of the ground and valence cationic molecules, Auger decay spectra calculations were performed. We found that fast bond scission leads to peak broadening of the spectra.

We demonstrate a novel experimental implementation to strongly align molecules at full repetition rates of free-electron lasers. We utilized the available in-house laser system at the coherent x-ray imaging beamline at the linac coherent light source. Chirped laser pulses, i.e., the direct output from the regenerative amplifier of the Ti:Sa chirped pulse amplification laser system, were used to strongly align 2, 5-diiodothiophene molecules in a molecular beam. The alignment laser pulses had pulse energies of a few mJ and a pulse duration of 94 ps. A degree of alignment of $\langle {\mathrm{cos}}^{2}{\theta }_{2{\rm{D}}}\rangle =0.85$ was measured, limited by the intrinsic temperature of the molecular beam rather than by the available laser system. With the general availability of synchronized chirped-pulse-amplified near-infrared laser systems at short-wavelength laser facilities, our approach allows for the universal preparation of molecules tightly fixed in space for experiments with x-ray pulses.

The recent availability of intense and ultrashort extreme ultraviolet sources opens up the possibility of investigating ultrafast electronic relaxation processes in matter in an unprecedented regime. In this work we report on the observation of two-photon excitation of interatomic Coulombic decay (ICD) in neon dimers using the tunable intense pulses delivered by the free electron laser FERMI. The unique characteristics of FERMI (narrow bandwidth, spectral stability, and tunability) allow one to resonantly excite specific ionization pathways and to observe a clear signature of the ICD mechanism in the ratio of the ion yield created by Coulomb explosion. The present experimental results are explained by ab initio electronic structure and nuclear dynamics calculations.

Recently, coherent x-ray sources have promoted developments of optical systems for focusing, imaging, and interferometers. In this paper, we propose a two-stage focusing optical system with the goal of achromatically focusing pulses from an x-ray free-electron laser (XFEL), with a focal width of 10 nm. In this optical system, the x-ray beam is expanded by a grazing-incidence aspheric mirror, and it is focused by a mirror that is shaped as a solid of revolution. We describe the design procedure and discuss the theoretical focusing performance. In theory, soft-XFEL lights can be focused to a 10 nm area without chromatic aberration and with high reflectivity; this creates an unprecedented power density of 10²⁰ W cm⁻² in the soft-x-ray range.

Competing multi-photon ionization processes, some leading to the formation of double core hole states, have been examined in 4-aminophenol. The experiments used the linac coherent light source (LCLS) x-ray free electron laser, in combination with a time-of-flight magnetic bottle electron spectrometer and the correlation analysis method of covariance mapping. The results imply that 4-aminophenol molecules exposed to the focused x-ray pulses of the LCLS sequentially absorb more than two x-ray photons, resulting in the formation of multiple core holes as well as in the sequential removal of photoelectrons and Auger electrons (so-called PAPA sequences).

We provide a detailed quantitative study of the possible role of a small admixture of harmonics on resonant two-photon ionization. The motivation comes from the occasional presence of 2nd and 3rd harmonics in FEL radiation. We obtain the dependence of ionic yields on the intensity of the fundamental, the percentage of 2nd harmonic and the detuning of the fundamental from resonance. Having examined the cases of one and two intermediate resonances, we arrive at results of general validity and global behaviour, showing that even a small amount of harmonic may seem deceptively innocuous.

Recent advances in x-ray free-electron lasers (XFELs) open up new pathways for contributing to industrial research-and-development activities. In this article, we describe our initiatory attempt at using the SPring-8 Ångström compact free-electron laser (SACLA) for industrial applications. The attempt was conducted by the authors through the industry-academia partnership program initiated by RIKEN, aimed at examining the potential of XFELs for the analysis of car-related nanomaterials. Using the infrastructures developed at SACLA, we performed single-shot coherent diffractive imaging experiments on automotive exhaust catalysts and succeeded in obtaining the reconstructed images. This effort has paved the way for the future use of XFELs in the research-and-development activity of automotive exhaust catalysts.

We report the first measurement of the near oxygen K-edge auger spectrum of the glycine molecule. Our work employed an x-ray free electron laser as the photon source operated with input photon energies tunable between 527 and 547 eV. Complete electron spectra were recorded at each photon energy in the tuning range, revealing resonant and non-resonant auger structures. Finally ab initio theoretical predictions are compared with the measured above the edge auger spectrum and an assignment of auger decay channels is performed.

Free electron laser light sources delivering high intensity pulses of short wavelength radiation are opening novel possibilities for the investigation of matter at the nanoscale and for the discovery and understanding of new physical processes occurring at the exotic transient states they make accessible. Strong ionization of atomic constituents of a nano-sized sample is a representative example of such processes and the understanding of ionization dynamics is crucial for a realistic description of the experiments. We report here on multiple ionization experiments on free clusters of titanium, a high cohesive energy metal. The time of flight ion spectra reveal a saturation of the cluster ionization at ∼10¹⁶ photons per pulse per cm². Our results also show a clear lack of any explosion process, opposite to what is observed for a rare-gas cluster under similar conditions. A simple and generalized multi-step ionization model including Coulomb frustration of the photoemission process effectively reproduces with a good agreement the main features of the experimental observation and points to an interpretation of the data involving a substantial energy deposition into the cluster through electronic system heating upon scattering events within photoemission.

We introduce a complex scaling discrete dipole approximation (CSDDA) method and study single-shot x-ray diffraction patterns from non-spherical, absorbing nanotargets in the limit of linear response. The convergence of the employed Born series-based iterative solution of the discrete dipole approximation problem via optimal complex mixing turns out to be substantially faster than the original approach with real-valued mixing coefficients, without additional numerical effort per iteration. The CSDDA method is employed to calculate soft x-ray diffraction patterns from large icosahedral silver nanoparticles with diameters up to about $250\;\mathrm{nm}$. Our analysis confirms the requirement of relatively long wavelengths to map truly 3D structure information to the experimentally accessible regions of 2D scattering images. On the other hand, we show that short wavelengths are preferable to retain visibility of fine structures such as interference fringes in the scattering patterns when using ultrashort x-ray pulses in the attosecond domain. A simple model is presented to estimate the minimal pulse duration below which the fringe contrast vanishes. Knowledge of the impact of the bandwidth of short pulses on the diffraction images is important to extract information on ultrafast dynamical processes from time-resolved x-ray diffractive imaging experiments on free nanoparticles, in particular at long wavelengths.

Ionization dynamics of resonantly excited helium nanodroplets have been studied by intense XUV light. By doping the nanodroplets with atoms that either attach to the surface or submerge into the center of the droplet, one can study the dynamics of excitation and ionization through the droplet. When resonantly exciting the droplet, we observe a strong ionization enhancement for atoms attached to the surface. On the other hand, atoms embedded inside the nanodroplet are less efficiently ionized. We attribute this effect to an ultrafast energy transfer to the surface of the droplet and subsequent Penning ionization of the surface-bound dopant.

Single particle imaging (SPI) is one of the front-page opportunities which were used to motivate the construction of the first x-ray free electron lasers (XFELs). SPI's big advantage is that it avoids radiation damage to biological samples because the diffraction takes place in femtosecond single shots before any atomic motion can take place in the sample, hence before the onset of radiation damage. This is the 'diffract before destruction' theme, destruction being assured from the high x-ray doses used. This article reports our collaboration's first attempt at SPI using the SACLA XFEL facility in June 2015. The report is limited to experience with the instrumentation and examples of data because we have not yet had time to invert them to images.

We theoretically investigate the laser-assisted photoionization of He by an extreme ultra violet (XUV) pulse in the presence of a linearly chirped intense laser pulse by solving the time-dependent Schrödinger equation within the single-active-electron approximation. Analysis based on the time-dependent perturbation theory is also carried out to provide more physical insights. A new scheme is shown to be capable of extracting the arrival time of an XUV free-electron laser (FEL) pulse relative to an external laser pulse as well as the XUV pulse duration from the photoelectron sidebands resulting from XUV ionization in the presence of a chirped laser pulse. This scheme is independent of the energy fluctuation and the timing jittering of the FEL pulse. Therefore it can be implemented in a non-invasive way to characterize FEL pulses on a shot-by-shot basis in time-resolved spectroscopy.

We have measured electron energy spectra and asymmetry parameters of Ar clusters and Xe clusters illuminated by intense x-rays at 5 and 5.5 keV. A velocity map imaging spectrometer was developed for this purpose and employed at an x-ray free-electron laser facility, SACLA in Japan. The cluster size dependence and the peak fluence dependence of the electron spectra and asymmetry parameters are discussed.

Single-shot imaging using femtosecond x-ray pulses from x-ray free electron lasers (XFELs) has revealed high-resolution structures of Au nanoparticles and biological macromolecular complexes. The x-ray pulse power of 10 GW is enough to vaporize specimen when it is focused on a few microns area. This makes it essential to have a single particle loader to provide fresh samples to the x-ray pulses. In this paper we introduce single-shot imaging at Spring-8 Angstrom Compact Free Electron Laser (SACLA) to investigate various types of specimen, from metallic nanoparticles to biological macromolecules, prepared on Si₃N₄ membrane. A significant reduction in sample consumption is achieved while maintaining a data acquisition rate of 30 Hz, which is compatible with the current SACLA operation rate.