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Because of their high photon flux, X-ray free-electron lasers (FEL) allow to resolve the structure of individual nanoparticles via coherent diffractive imaging (CDI) within a single X-ray pulse. Since the inevitable rapid destruction of the sample limits the achievable resolution, a thorough understanding of the spatiotemporal evolution of matter on the nanoscale following the irradiation is crucial. We present a technique to track X-ray induced structural changes in time and space by recording two consecutive diffraction patterns of the same single, free-flying nanoparticle, acquired separately on two large-area detectors opposite to each other, thus examining both the initial and evolved particle structure. We demonstrate the method at the extreme ultraviolet (XUV) and soft X-ray Free-electron LASer in Hamburg (FLASH), investigating xenon clusters as model systems. By splitting a single XUV pulse, two diffraction patterns from the same particle can be obtained. For focus intensities of about $2\cdot10^{12}\,\text{W/cm}^2$ we observe still largely intact clusters even at the longest delays of up to 650 picoseconds of the second pulse, indicating that in the highly absorbing systems the damage remains confined to one side of the cluster. Instead, in case of five times higher flux, the diffraction patterns show clear signatures of disintegration, namely increased diameters and density fluctuations in the fragmenting clusters. Future improvements to the accessible range of dynamics and time resolution of the approach are discussed.

The free expansion of a planar plasma surface is a fundamental non-equilibrium process relevant for various fields but as-yet experimentally still difficult to capture. The significance of the associated spatiotemporal plasma motion ranges from astrophysics and controlled fusion to laser machining, surface high-harmonic generation, plasma mirrors, and laser-particle acceleration. Here, we show that x-ray coherent diffractive imaging can surpass existing approaches and enables the quantitative real-time analysis of the sudden free expansion of nanoplasmas. For laser-ionized SiO$_2$ nanospheres, we resolve the formation of the emerging nearly self-similar plasma profile evolution and expose the so far inaccessible shell-wise expansion dynamics including the associated startup delay and rarefaction front velocity. Our results establish time-resolved diffractive imaging as an accurate quantitative diagnostic platform for tracing and characterizing plasma expansion and indicate the possibility to resolve various laser-driven processes including shock formation and wave-breaking phenomena with unprecedented resolution.

The possibility of suddenly ionized molecules undergoing extremely fast electron hole dynamics prior to significant structural change was first recognized more than 20 years ago and termed charge migration. The accurate probing of ultrafast electron hole dynamics requires measurements that have both sufficient temporal resolution and can detect the localization of a specific hole within the molecule. We report an investigation of the dynamics of inner valence hole states in isopropanol where we use an x-ray pump/x-ray probe experiment, with site and state-specific probing of a transient hole state localized near the oxygen atom in the molecule, together with an ab initio theoretical treatment. We record the signature of transient hole dynamics and make the first observation of dynamics driven by frustrated Auger-Meitner transitions. We verify that the hole lifetime is consistent with our theoretical prediction. This state-specific measurement paves the way to widespread application for observations of transient hole dynamics localized in space and time in molecules and thus to charge transfer phenomena that are fundamental in chemical and material physics.

Intense X-ray free-electron lasers (XFELs) can rapidly excite matter, leaving it in inherently unstable states that decay on femtosecond timescales. As the relaxation occurs primarily via Auger emission, excited state observations are constrained by Auger decay. In situ measurement of this process is therefore crucial, yet it has thus far remained elusive at XFELs due to inherent timing and phase jitter, which can be orders of magnitude larger than the timescale of Auger decay. Here, we develop a new approach termed self-referenced attosecond streaking, based upon simultaneous measurements of streaked photo- and Auger electrons. Our technique enables sub-femtosecond resolution in spite of jitter. We exploit this method to make the first XFEL time-domain measurement of the Auger decay lifetime in atomic neon, and, by using a fully quantum-mechanical description, retrieve a lifetime of $2.2^{ + 0.2}_{ - 0.3}$ fs for the KLL decay channel. Importantly, our technique can be generalised to permit the extension of attosecond time-resolved experiments to all current and future FEL facilities., Comment: Main text: 20 pages, 3 figures. Supplementary information: 17 pages, 6 figures

Novel perspectives of controlling molecular systems have recently arisen from the possibility of generating attosecond pulses in the ultraviolet regime and tailoring electron dynamics in its natural time scale. The cornerstone mechanism is the so-called charge migration, he production of a coherent charge transfer with subfemtosecond oscillations across a molecule. Typically, charge migration is induced by the ionization of valence molecular orbitals. However, recent technological developments allow the generation of attosecond pulses in the x-ray regime. In this case, the absorption of photons creates core-hole states. In light elements, core-hole states mainly decay by Auger processes that, driven by electron correlations, involve valence orbitals. We theoretically demonstrate in a fluoroacetylene molecule a double-hole charge migration triggered by attosecond core-electron photoionization, followed by Auger electron relaxations. This opens a new route for inducing with x rays charge transfer processes in the subfemtosecond time scale.

The capability of generating two intense, femtosecond x-ray pulses with controlled time delay opens the possibility of performing time-resolved experiments for x-ray induced phenomena. We have applied this capability to study the photoinduced dynamics in diatomic molecules. In molecules composed of low-Z elements, \textit{K}-shell ionization creates a core-hole state in which the main decay mode is an Auger process involving two electrons in the valence shell. After Auger decay, the nuclear wavepackets of the transient two-valence-hole states continue evolving on the femtosecond timescale, leading either to separated atomic ions or long-lived quasi-bound states. By using an x-ray pump and an x-ray probe pulse tuned above the \textit{K}-shell ionization threshold of the nitrogen molecule, we are able to observe ion dissociation in progress by measuring the time-dependent kinetic energy releases of different breakup channels. We simulated the measurements on N$_2$ with a molecular dynamics model that accounts for \textit{K}-shell ionization, Auger decay, and the time evolution of the nuclear wavepackets. In addition to explaining the time-dependent feature in the measured kinetic energy release distributions from the dissociative states, the simulation also reveals the contributions of quasi-bound states.

Arbitrary manipulation of the temporal and spectral properties of X-ray pulses at free-electron lasers (FELs) would revolutionize many experimental applications. At the Linac Coherent Light Source at Stanford National Accelerator Laboratory, the momentum phase-space of the FEL driving electron bunch can be tuned to emit a pair of X-ray pulses with independently variable photon energy and femtosecond delay. However, while accelerator parameters can easily be adjusted to tune the electron bunch phase-space, the final impact of these actuators on the X-ray pulse cannot be predicted with sufficient precision. Furthermore, shot-to-shot instabilities that distort the pulse shape unpredictably cannot be fully suppressed. Therefore, the ability to directly characterize the X-rays is essential to ensure precise and consistent control. In this work, we have generated X-ray pulse pairs and characterized them on a single-shot basis with femtosecond resolution through time-resolved photoelectron streaking spectroscopy. This achievement completes an important step toward future X-ray pulse shaping techniques.

Organic chromophores with heteroatoms possess an important excited state relaxation channel from an optically allowed {\pi}{\pi}* to a dark n{\pi}*state. We exploit the element and site specificity of soft x-ray absorption spectroscopy to selectively follow the electronic change during the {\pi}{\pi}*/n{\pi}* internal conversion. As a hole forms in the n orbital during {\pi}{\pi}*/n{\pi}* internal conversion, the near edge x-ray absorption fine structure (NEXAFS) spectrum at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept with the nucleobase thymine, a prototypical heteroatomic chromophore. With the help of time resolved NEXAFS spectroscopy at the oxygen K-edge, we unambiguously show that {\pi}{\pi}*/n{\pi}* internal conversion takes place within (60 \pm 30) fs. High-level coupled cluster calculations on the isolated molecules used in the experiment confirm the superb electronic structure sensitivity of this new method for excited state investigations.

X-ray free-electron lasers (XFELs) are the only sources currently able to produce bright few-fs pulses with tunable photon energies from 100 eV to more than 10 keV. Due to the stochastic SASE operating principles and other technical issues the output pulses are subject to large fluctuations, making it necessary to characterize the x-ray pulses on every shot for data sorting purposes. We present a technique that applies machine learning tools to predict x-ray pulse properties using simple electron beam and x-ray parameters as input. Using this technique at the Linac Coherent Light Source (LCLS), we report mean errors below 0.3 eV for the prediction of the photon energy at 530 eV and below 1.6 fs for the prediction of the delay between two x-ray pulses. We also demonstrate spectral shape prediction with a mean agreement of 97%. This approach could potentially be used at the next generation of high-repetition-rate XFELs to provide accurate knowledge of complex x-ray pulses at the full repetition rate., Comment: 12 pages, 8 figures

This paper gives an account of our progress towards performing femtosecond time-resolved photoelectron diffraction on gas-phase molecules in a pump-probe setup combining optical lasers and an X-ray Free-Electron Laser. We present results of two experiments aimed at measuring photoelectron angular distributions of laser-aligned 1-ethynyl-4-fluorobenzene (C8H5F) and dissociating, laseraligned 1,4-dibromobenzene (C6H4Br2) molecules and discuss them in the larger context of photoelectron diffraction on gas-phase molecules. We also show how the strong nanosecond laser pulse used for adiabatically laser-aligning the molecules influences the measured electron and ion spectra and angular distributions, and discuss how this may affect the outcome of future time-resolved photoelectron diffraction experiments., Comment: 24 pages, 10 figures, Faraday Discussions 171

We investigate the creation of double K-shell holes in N2 molecules via sequential absorption of two photons on a timescale shorter than the core-hole lifetime by using intense x-ray pulses from the Linac Coherent Light Source free electron laser. The production and decay of these states is characterized by photoelectron spectroscopy and Auger electron spectroscopy. In molecules, two types of double core holes are expected, the first with two core holes on the same N atom, and the second with one core hole on each N atom. We report the first direct observations of the former type of core hole in a molecule, in good agreement with theory, and provide an experimental upper bound for the relative contribution of the latter type., Comment: 5 pages, 3 figures

We present a new method for ultrafast spectroscopy of molecular photoexcited dynamics. The technique uses a pair of femtosecond pulses: a photoexcitation pulse initiating excited state dynamics followed by a soft x-ray (SXR) probe pulse that core ionizes certain atoms inside the molecule. We observe the Auger decay of the core hole as a function of delay between the photoexcitation and SXR pulses. The core hole decay is particularly sensitive to the local valence electrons near the core and shows new types of propensity rules, compared to dipole selection rules in SXR absorption or emission spectroscopy. We apply the delayed ultrafast x-ray Auger probing (DUXAP) method to the specific problem of nucleobase photoprotection to demonstrate its potential. The ultraviolet photoexcited \pi\pi* states of nucleobases are prone to chemical reactions with neighboring bases. To avoid this, the single molecules funnel the \pi\pi* population to lower lying electronic states on an ultrafast timescale under violation of the Born-Oppenheimer approximation. The new type of propensity rule, which is confirmed by Auger decay simulations, allows us to have increased sensitivity on the direct relaxation from the \pi\pi* state to the vibrationally hot electronic ground state. For the nucleobase thymine, we measure a decay constant of 300 fs in agreement with previous quantum chemical simulations.

We have performed X-ray two-photon photoelectron spectroscopy (XTPPS) using the Linac Coherent Light Source (LCLS) X-ray free-electron laser (FEL) in order to study double core-hole (DCH) states of CO2, N2O and N2. The experiment verifies the theory behind the chemical sensitivity of two-site (ts) DCH states by comparing a set of small molecules with respect to the energy shift of the tsDCH state and by extracting the relevant parameters from this shift., Comment: 11 pages, 2 figures

We present the results of an experiment where amorphous carbon was irradiated by femtosecond x-ray free electron laser pulses. The 830 eV laser pulses induce a phase transition in the material which is characterized ex-situ. The phase transition energy threshold is determined by measuring the surface of each irradiated area using an optical Nomarski microscope. The threshold fluence is found to be 282 +/- 11 mJ/cm^2, corresponding to an absorbed dose at the surface of 131 +/-5 meV/atom. Atomic force microscopy measurements show volume expansion of the irradiated sample area, suggesting a solid to solid phase transition. Deeper insight into the phase transition is gained by using scanning photoelectron microscopy and micro-Raman spectroscopy. Photoelectron microscopy shows graphitization, i.e. modification from sp3 to sp2 hybridization, of the irradiated material. The micro-Raman spectra show the appearance of local order, i.e. formation of graphite nanocrystals. Finally, the nature of the phase transition is discussed, taking into account previous theory and experimental results.