A sub-100†nm thickness flat jet for extreme ultraviolet to soft X-ray absorption spectroscopy.

Experimental characterization of the structural, electronic and dynamic properties of dilute systems in aqueous solvents, such as nanoparticles, molecules and proteins, are nowadays an open challenge. X-ray absorption spectroscopy (XAS) is probably one of the most established approaches to this aim as it is element-specific. However, typical dilute systems of interest are often composed of light elements that require extreme-ultraviolet to soft X-ray photons. In this spectral regime, water and other solvents are rather opaque, thus demanding radical reduction of the solvent volume and removal of the liquid to minimize background absorption. Here, we present an experimental endstation designed to operate a liquid flat jet of sub-micrometre thickness in a vacuum environment compatible with extreme ultraviolet/soft XAS measurements in transmission geometry. The apparatus developed can be easily connected to synchrotron and free-electron-laser user-facility beamlines dedicated to XAS experiments. The conditions for stable generation and control of the liquid flat jet are analyzed and discussed. Preliminary soft XAS measurements on some test solutions are shown.

Superradiant Thomson scattering from graphite in the extreme ultraviolet.

We study the Thomson scattering from highly oriented pyrolitic graphite excited by the extreme ultraviolet, coherent pulses of FERMI free electron laser (FEL). An apparent nonlinear behavior is observed and fully described in terms of the coherent nature of both exciting FEL beam and scattered radiation, producing an intensity-dependent enhancement of the Thomson scattering cross-section. The process resembles Dicke's superradiant phenomenon and is thus interpreted as the observation of superradiant Thomson scattering. The process also triggers the creation of coherent, low-q ([Formula: see text] 0.3 Å[Formula: see text]), low energy phonons. The experimental data and analysis provide quantitative information on the sample characteristics, absorption, scattering factor, and coherent phonon energies and populations and open the route for the investigation of the deep nature of complex materials.

Saturable Absorption of Free-Electron Laser Radiation by Graphite near the Carbon K-Edge.

The interaction of intense light with matter gives rise to competing nonlinear responses that can dynamically change material properties. Prominent examples are saturable absorption (SA) and two-photon absorption (TPA), which dynamically increase and decrease the transmission of a sample depending on pulse intensity, respectively. The availability of intense soft X-ray pulses from free-electron lasers (FELs) has led to observations of SA and TPA in separate experiments, leaving open questions about the possible interplay between and relative strength of the two phenomena. Here, we systematically study both phenomena in one experiment by exposing graphite films to soft X-ray FEL pulses of varying intensity. By applying real-time electronic structure calculations, we find that for lower intensities the nonlinear contribution to the absorption is dominated by SA attributed to ground-state depletion; our model suggests that TPA becomes more dominant for larger intensities (>1014 W/cm2). Our results demonstrate an approach of general utility for interpreting FEL spectroscopies.

Angstrom-Resolved Interfacial Structure in Buried Organic-Inorganic Junctions.

Charge transport processes at interfaces play a crucial role in many processes. Here, the first soft x-ray second harmonic generation (SXR SHG) interfacial spectrum of a buried interface (boron-Parylene N) is reported. SXR SHG shows distinct spectral features that are not observed in x-ray absorption spectra, demonstrating its extraordinary interfacial sensitivity. Comparison to electronic structure calculations indicates a boron-organic separation distance of 1.9 Å, with changes of less than 1 Å resulting in easily detectable SXR SHG spectral shifts (ca. hundreds of milli-electron volts).

Non-linear self-driven spectral tuning of Extreme Ultraviolet Femtosecond Pulses in monoatomic materials.

Self-action nonlinearity is a key aspect - either as a foundational element or a detrimental factor - of several optical spectroscopies and photonic devices. Supercontinuum generation, wavelength converters, and chirped pulse amplification are just a few examples. The recent advent of Free Electron Lasers (FEL) fostered building on nonlinearity to propose new concepts and extend optical wavelengths paradigms for extreme ultraviolet (EUV) and X-ray regimes. No evidence for intrapulse dynamics, however, has been reported at such short wavelengths, where the light-matter interactions are ruled by the sharp absorption edges of core electrons. Here, we provide experimental evidence for self-phase modulation of femtosecond FEL pulses, which we exploit for fine self-driven spectral tunability by interaction with sub-micrometric foils of selected monoatomic materials. Moving the pulse wavelength across the absorption edge, the spectral profile changes from a non-linear spectral blue-shift to a red-shifted broadening. These findings are rationalized accounting for ultrafast ionization and delayed thermal response of highly excited electrons above and below threshold, respectively.

Ultrafast Dynamics of Plasmon-Mediated Charge Transfer in Ag@CeO2 Studied by Free Electron Laser Time-Resolved X-ray Absorption Spectroscopy.

Expanding the activity of wide bandgap semiconductors from the UV into the visible range has become a central goal for their application in green solar photocatalysis. The hybrid plasmonic/semiconductor system, based on silver nanoparticles (Ag NPs) embedded in a film of CeO2, is an example of a functional material developed with this aim. In this work, we take advantage of the chemical sensitivity of free electron laser (FEL) time-resolved soft X-ray absorption spectroscopy (TRXAS) to investigate the electron transfer process from the Ag NPs to the CeO2 film generated by the NPs plasmonic resonance photoexcitation. Ultrafast changes (<200 fs) of the Ce N4,5 absorption edge allowed us to conclude that the excited Ag NPs transfer electrons to the Ce atoms of the CeO2 film through a highly efficient electron-based mechanism. These results demonstrate the potential of FEL-based TRXAS measurements for the characterization of energy transfer in novel hybrid plasmonic/semiconductor materials.

Timing methodologies and studies at the FERMI free-electron laser.

Time-resolved investigations have begun a new era of chemistry and physics, enabling the monitoring in real time of the dynamics of chemical reactions and matter. Induced transient optical absorption is a basic ultrafast electronic effect, originated by a partial depletion of the valence band, that can be triggered by exposing insulators and semiconductors to sub-picosecond extreme-ultraviolet pulses. Besides its scientific and fundamental implications, this process is very important as it is routinely applied in free-electron laser (FEL) facilities to achieve the temporal superposition between FEL and optical laser pulses with tens of femtoseconds accuracy. Here, a set of methodologies developed at the FERMI facility based on ultrafast effects in condensed materials and employed to effectively determine the FEL/laser cross correlation are presented.

High resolution beam profiling of X-ray free electron laser radiation by polymer imprint development.

High resolution metrology of beam profiles is presently a major challenge at X-ray free electron lasers. We demonstrate a characterization method based on beam imprints in poly (methyl methacrylate). By immersing the imprints formed at 47.8 eV into organic solvents, the regions exposed to the beam are removed similar to resist development in grayscale lithography. This allows for extending the sensitivity of the method by more than an order of magnitude compared to the established analysis of imprints created solely by ablation. Applying the Beer-Lambert law for absorption, the intensity distribution in a micron-sized focus can be reconstructed from one single shot with a high dynamic range, exceeding 103. The procedure described here allows for beam characterization at free electron lasers revealing even faint beam tails, which are not accessible when using ablation imprint methods. We demonstrate the greatly extended dynamic range on developed imprints taken in focus of conventional Fresnel zone plates and spiral zone plates producing beams with a topological charge.

EUV stimulated emission from MgO pumped by FEL pulses.

Stimulated emission is a fundamental process in nature that deserves to be investigated and understood in the extreme ultra-violet (EUV) and x-ray regimes. Today, this is definitely possible through high energy density free electron laser (FEL) beams. In this context, we give evidence for soft-x-ray stimulated emission from a magnesium oxide solid target pumped by EUV FEL pulses formed in the regime of travelling-wave amplified spontaneous emission in backward geometry. Our results combine two effects separately reported in previous works: emission in a privileged direction and existence of a material-dependent threshold for the stimulated emission. We develop a novel theoretical framework, based on coupled rate and transport equations taking into account the solid-density plasma state of the target. Our model accounts for both observed mechanisms that are the privileged direction for the stimulated emission of the Mg L2,3 characteristic emission and the pumping threshold.

Toward an integrated device for spatiotemporal superposition of free-electron lasers and laser pulses.

Free-electron lasers (FELs) currently represent a step forward on time-resolved investigations on any phase of matter through pump-probe methods involving FELs and laser beams. That class of experiments requires an accurate spatial and temporal superposition of pump and probe beams on the sample, which at present is still a critical procedure. More efficient approaches are demanded to quickly achieve the superposition and synchronization of the beams. Here, we present what we believe is a novel technique based on an integrated device allowing the simultaneous characterization and the fast spatial and temporal overlapping of the beams, reducing the alignment procedure from hours to minutes.

A novel approach in the free-electron laser diagnosis based on a pixelated phosphor detector.

A new high-performance method for the free-electron laser (FEL) focused beam diagnosis has been successfully tested at the FERMI FEL in Trieste, Italy. The novel pixelated phosphor detector (PPD) consists of micrometric pixels produced by classical UV lithography and dry etching technique, fabricated on a silicon substrate, arranged in a hexagonal geometry and filled with suitable phosphors. It has been demonstrated that the overall resolution of the system has increased by reducing the diffusion of the light in the phosphors. Various types of PPD have been produced and tested, demonstrating a high resolution in the beam profile and the ability to measure the actual spot size shot-to-shot with an unprecedented resolution. For these reasons, the proposed detector could become a reference technique in the FEL diagnosis field.

Experimental setups for FEL-based four-wave mixing experiments at FERMI.

The recent advent of free-electron laser (FEL) sources is driving the scientific community to extend table-top laser research to shorter wavelengths adding elemental selectivity and chemical state specificity. Both a compact setup (mini-TIMER) and a separate instrument (EIS-TIMER) dedicated to four-wave-mixing (FWM) experiments has been designed and constructed, to be operated as a branch of the Elastic and Inelastic Scattering beamline: EIS. The FWM experiments that are planned at EIS-TIMER are based on the transient grating approach, where two crossed FEL pulses create a controlled modulation of the sample excitations while a third time-delayed pulse is used to monitor the dynamics of the excited state. This manuscript describes such experimental facilities, showing the preliminary results of the commissioning of the EIS-TIMER beamline, and discusses original experimental strategies being developed to study the dynamics of matter at the fs-nm time-length scales. In the near future such experimental tools will allow more sophisticated FEL-based FWM applications, that also include the use of multiple and multi-color FEL pulses.

EIS: the scattering beamline at FERMI.

The Elastic and Inelastic Scattering (EIS) beamline at the free-electron laser FERMI is presented. It consists of two separate end-stations: EIS-TIMEX, dedicated to ultrafast time-resolved studies of matter under extreme and metastable conditions, and EIS-TIMER, dedicated to time-resolved spectroscopy of mesoscopic dynamics in condensed matter. The scientific objectives are discussed and the instrument layout illustrated, together with the results from first exemplifying experiments.

Slow-to-fast transition of hydrogen bond dynamics in acetamide hydration shell formation.

The formation of a hydration shell in acetamide aqueous solution has been investigated by means of UV Raman spectroscopy. The experimental results reveal the existence of two distinct regimes of water dynamics. At high acetamide concentration water molecules show a structural and dynamical behavior consistent with the so-called iceberg model. Upon increasing the amount of water we observe the formation of a hydration shell marked by fastening of hydrogen-bond dynamics. Such a behavior may help to shed light on the scientific debate on how water rearranges around the hydrophobic portions of solute molecules (iceberg vs. non-iceberg models).

Determination of dynamical parameters in liquids by homodyne transient grating spectroscopy at large angles.

We report on the possibility of extracting fast dynamical relaxation times from homodyne transient grating measurements. We demonstrate the validity of our approach by experimental measurements on liquid acetonitrile and by comparison with literature. This approach would be of tremendous help in the case of free-electron-laser-based transient grating experiments due to the overcoming of technical difficulties, such as large-angle geometries.

Towards jitter-free pump-probe measurements at seeded free electron laser facilities.

X-ray free electron lasers (FEL) coupled with optical lasers have opened unprecedented opportunities for studying ultrafast dynamics in matter. The major challenge in pump-probe experiments using FEL and optical lasers is synchronizing the arrival time of the two pulses. Here we report a technique that benefits from the seeded-FEL scheme and uses the optical seed laser for nearly jitter-free pump-probe experiments. Timing jitter as small as 6 fs has been achieved and confirmed by measurements of FEL-induced transient reflectivity changes of Si3N4 using both collinear and non-collinear geometries. Planned improvements of the experimental set-up are expected to further reduce the timing jitter between the two pulses down to fs level.

Thermodynamic hydration shell behavior of glycine.

Glycine aqueous solutions have been studied as a function of temperature and concentration by means of UV Brillouin and Raman spectroscopes. Brillouin spectra provided information on the average relaxation time τα related to the mechanisms of hydrogen bonds (HBs) formation and breaking. The concentration-temperature behavior of τ has been compared to the vibrational dephasing lifetime of atoms involved in HBs, as derived by a lineshape analysis of Raman spectra. We point out how it is possible to trace the thermodynamic behavior of a selected HB from Raman data. In particular, our results confirm the predominant role played in the hydration process by the water molecules surrounding the hydrophobic groups and, furthermore, evidence how at low temperature the HB strength between these molecules is greater than those found in bulk water and between glycine and water molecules.

Investigation of acetic acid hydration shell formation through Raman spectra line-shape analysis.

Raman spectra of acetic acid aqueous solutions in the 500-4000 cm(-1) range have been measured as a function of water concentration to investigate the hydration shell formation mechanism around the acetic acid molecules. A fitting procedure based on the Kubo-Anderson model has been applied to the spectra. This has allowed us to determine the average lifetime of the hydrogen bonds involving a given functional group, as well as their geometrical distribution as a function of water concentration. The comparison of our results with literature data has demonstrated that the fitting model is adequate to describe organic water mixtures. Finally, the role of water in the formation of the hydrophobic shell around the methyl group in diluted acetic acid water solutions has been discussed, evidencing how the methyl group hydrophobicity strongly influences the acetic acid behavior in aqueous solutions.

An XAS experimental approach to study low Pt content electrocatalysts operating in PEM fuel cells.

We present an X-ray absorption spectroscopy (XAS) study of a low Pt content catalyst layer (Pt loading 0.1 mg cm(-2)) operating at the cathode of a proton exchange membrane fuel cell (PEMFC). This catalyst is based on the use of a mesoporous inorganic matrix as a support for the catalyst Pt nanoparticles. Due to the high Pt dilution, in situ measurements of its structural properties by XAS are challenging and suitable experimental strategies must be devised for this purpose. In particular, we show that accurate XAS in situ fluorescence measurements can be obtained using an optimized fuel cell, suitable protocols for alignment of a focused X-ray beam and an appropriate filter for the background signal of the other atomic species contained in the electrodes. Details, advantages and limitations of the XAS technique for in situ measurements are discussed. Analysis of the near-edge XAS and EXAFS (extended X-ray absorption fine structure) data, corroborated by a HRTEM (high-resolution transmission electron microscopy) study, shows that the Pt particles have a local structure compatible with that of bulk Pt (fcc) and coordination numbers match those expected for particles with typical sizes in the 1.5-2.0 nm range. Substantial changes in the oxidation state and in local atomic arrangement of the Pt particles are found for different applied potentials. The catalyst support, containing W atoms, exhibits a partial reduction upon PEMFC activation, thus mimicking the catalyst behavior. This indicates a possible role of the mesoporous matrix in favouring the oxygen reduction reaction (ORR) and stimulates further research on active catalyst supports.

Nearest-neighbor oxygen distances in liquid water and ice observed by x-ray Raman based extended x-ray absorption fine structure.

We report the nearest-neighbor oxygen-oxygen radial distribution function (NN O-O RDF) of room temperature liquid water and polycrystalline ice Ih (-16.8 degrees C) obtained by x-ray Raman based extended x-ray absorption fine structure (EXAFS) spectroscopy. The spectra of the two systems were taken under identical experimental conditions using the same procedures to obtain the NN O-O RDFs. This protocol ensured a measurement of the relative distance distribution with very small systematic errors. The NN O-O RDF of water is found to be more asymmetric (tail extending to longer distances) with longer average distance (2.81 A for water and 2.76 A for ice) but a slightly shorter peak position (2.70 A for water and 2.71 A for ice). The refinement also showed a small but significant contribution from the linear O-H-O multiple scattering signal. The high sensitivity to short range distances of the EXAFS probe will set further restrictions to the range of possible models of liquid water.