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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).

Charge transport processes at interfaces which are governed by complexinterfacial electronic structure play a crucial role in catalytic reactions,energy storage, photovoltaics, and many biological processes. Here, the firstsoft X-ray second harmonic generation (SXR-SHG) interfacial spectrum of aburied interface (boron/Parylene-N) is reported. SXR-SHG shows distinctspectral features that are not observed in X-ray absorption spectra,demonstrating its extraordinary interfacial sensitivity. Comparison toelectronic structure calculations indicates a boron-organic separation distanceof 1.9 {\AA}, wherein changes as small as 0.1 {\AA} result in easily detectableSXR-SHG spectral shifts (ca. 100s of meV). As SXR-SHG is inherently ultrafastand sensitive to individual atomic layers, it creates the possibility to studya variety of interfacial processes, e.g. catalysis, with ultrafast timeresolution and bond specificity.

Ultrafast time-resolved extreme ultraviolet (EUV) reflectivity measurements of optically pumped amorphous carbon (a-C) have been performed with the FERMI free electron laser (FEL). This work extends the energy range used in previous reflectivity studies and adds polarization dependence. The EUV probe is known to be sensitive to lattice dynamics, since in this range the reflectivity is essentially unaffected by the photo-excited surface plasma. The exploitation of both s-and p-polarized EUV radiation permits variation of the penetration depth of the probe; a significant increase in the characteristic time is observed upon increasing the probing depth (1 vs. 5 ps) due to hydrodynamic expansion and consequent destruction of the excited region, implying that there is only a short window during which the probed region is in the isochoric regime. A weak wavelength dependence of the reflectivity is found, consistent with previous measurements and implying a maximum electronic temperature of 0.8 eV ± 0.4.

X-ray free-electron lasers (FELs), which amplify light emitted by a relativistic electron beam, are extending nonlinear optical techniques to shorter wavelengths, adding element specificity by exciting and probing electronic transitions from core levels. These techniques would benefit tremendously from having a stable FEL source, generating spectrally pure and wavelength-tunable pulses. We show that such requirements can be met by operating the FEL in the so-called echo-enabled harmonic generation (EEHG) configuration. Here, two external conventional lasers are used to precisely tailor the longitudinal phase space of the electron beam before emission of X-rays. We demonstrate high-gain EEHG lasing producing stable, intense, nearly fully coherent pulses at wavelengths as short as 5.9 nm (~211 eV) at the FERMI FEL user facility. Low sensitivity to electron-beam imperfections and observation of stable, narrow-band, coherent emission down to 2.6 nm (~474 eV) make the technique a prime candidate for generating laser-like pulses in the X-ray spectral region, opening the door to multidimensional coherent spectroscopies at short wavelengths.

We report an ab-initio study of a pump-probe experiment on the amino-acid glycine. We consider an UV pump followed by an X-ray probe tuned to carbon K-edge and study the vibronic structure of the core transition. The simulated experiment is feasible using existing free electron laser or high harmonic generation sources and thanks to the localization of the core orbitals posseses chemical selectivity. The present theory applies to other experimental schemes, including the use of a THz probe, available with present soft X-ray free electron lasers and/or high harmonic generation sources.

We have examined the transmission of soft X-ray pulses from the FERMI free electron laser through carbon films of varying thickness, quantifying nonlinear effects of pulses above and below the carbon K-edge. At typical of soft X-ray free electron laser intensities, pulses exhibit linear absorption at photon energies above and below the K-edge, ∼308 and ∼260 eV, respectively; whereas two-photon absorption becomes significant slightly below the K-edge, ∼284.2 eV. The measured two-photon absorption cross section at 284.18 eV (∼6 × 10−48 cm4 s) is 7 orders of magnitude above what is expected from a simple theory based on hydrogen-like atoms - a result of resonance effects.

X-ray free-electron lasers (XFELs) and table-top sources of x-rays based upon high harmonic generation (HHG) have revolutionized the field of ultrafast x-ray atomic and molecular physics, largely due to an explosive growth in capabilities in the past decade. XFELs now provide unprecedented intensity (1020 W cm-2) of x-rays at wavelengths down to ∼1 Ångstrom, and HHG provides unprecedented time resolution (∼50 attoseconds) and a correspondingly large coherent bandwidth at longer wavelengths. For context, timescales can be referenced to the Bohr orbital period in hydrogen atom of 150 attoseconds and the hydrogen-molecule vibrational period of 8 femtoseconds; wavelength scales can be referenced to the chemically significant carbon K-edge at a photon energy of ∼280 eV (44 Ångstroms) and the bond length in methane of ∼1 Ångstrom. With these modern x-ray sources one now has the ability to focus on individual atoms, even when embedded in a complex molecule, and view electronic and nuclear motion on their intrinsic scales (attoseconds and Ångstroms). These sources have enabled coherent diffractive imaging, where one can image non-crystalline objects in three dimensions on ultrafast timescales, potentially with atomic resolution. The unprecedented intensity available with XFELs has opened new fields of multiphoton and nonlinear x-ray physics where behavior of matter under extreme conditions can be explored. The unprecedented time resolution and pulse synchronization provided by HHG sources has kindled fundamental investigations of time delays in photoionization, charge migration in molecules, and dynamics near conical intersections that are foundational to AMO physics and chemistry. This roadmap coincides with the year when three new XFEL facilities, operating at Ångstrom wavelengths, opened for users (European XFEL, Swiss-FEL and PAL-FEL in Korea) almost doubling the present worldwide number of XFELs, and documents the remarkable progress in HHG capabilities since its discovery roughly 30 years ago, showcasing experiments in AMO physics and other applications. Here we capture the perspectives of 17 leading groups and organize the contributions into four categories: ultrafast molecular dynamics, multidimensional x-ray spectroscopies; high-intensity x-ray phenomena; attosecond x-ray science.

We present an extreme ultraviolet (EUV) transient grating (TG) experiment of the spinel Co3O4 compound using tuneable incident energies across the Co M2,3-edge and a 395 nm probe pulse, detecting both the first and the second diffraction orders (SDOs). While the first diffraction order shows a monotonous behavior as a function of time, with a sharp response at t = 0, followed by a weak sub-picosecond component and a nearly constant signal thereafter, the time dependence of SDO varies dramatically with the incident energy as it is tuned across the Co M-edge, with the appearance of a component at t > 1 ps that grows with increasing energy. The results are rationalized in terms of the deviations of the initial grating from sinusoidal to non-sinusoidal, namely a flattening of the grating pattern, that introduces new Fourier components. These deviations are due to higher order, three-body terms in the population relaxation kinetics. The present results highlight the use of the SDO response in EUV TG as a tool to identify higher order terms in the population kinetics. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

G-quadruplexes (G4s) are noncanonical forms of DNA involved in many key genome functions. Here, we exploited UV Resonance Raman scattering to simultaneously explore the vibrational behavior of a human telomeric G4 (Tel22) and its aqueous solvent as the biomolecule underwent thermal melting. We found that the OH stretching band, related to the local hydrogen-bonded network of a water molecule, was in strict relation with the vibrational features of the G4 structure as a function of temperature. In particular, the modifications to the tetrahedral ordering of the water network were strongly coupled to the DNA rearrangements, showing changes in temperature that mirrored the multi-step melting process of Tel22. The comparison between circular dichroism and Raman results supported this view. The present findings provide novel insights into the impact of the molecular environment on G4 conformation. Improving current knowledge on the solvent structural properties will also contribute to a better understanding of the role played by water arrangement in the complexation of G4s with ligands. [ABSTRACT FROM AUTHOR]

The characterization of thermal and elastic properties at the nanometer length scale is fundamental for the implementation of materials in nanotechnology. Here, we show how four-wave mixing of extreme ultraviolet ultrashort pulses allows for high-precision measurements of nanoscale elasticity in thin suspended silicon nitride membranes through the generation and detection of Lamb waves at 10's of nm wavelengths. Our approach is contact-free and nondestructive, and it provides an estimate of both shear and longitudinal elastic moduli, without the need of nanopatterning. The data provide important information on nanoscale thermal transport and reveal a heat carrier behavior compatible with the diffusive regime. By controlling the fluence of the free-electron laser excitation pulses, we study the dependence of elastic moduli and the thermal relaxation rate on the sample temperature, which increases by hundreds of kelvins due to radiation absorption. At the same time, the experimental data allow us to estimate the characteristic time of phonon attenuation. The capability of determining this parameter, as well as the elastic moduli, at nanoscale wavelengths is a key aspect for the fundamental understanding of solids without translational invariance. [ABSTRACT FROM AUTHOR]

The utility of ionic liquids (ILs) as alternative solvents for stabilizing and preserving the native structure of DNA over the long term may be envisaged for biotechnological and biomedical applications in the near future. The delicate balance between the stabilizing and destabilizing effects of IL-mediated interactions with the structure of DNA is complex and is still not well understood. This work reports a fundamental study dealing with the effect exerted by cations and anions in imidazolium-based ILs on the thermal structural stability of large nucleic acid molecules. Multi-wavelength UV resonance Raman spectroscopy is used for selectively detecting heat-induced structural transitions of DNA localized on specific base tracts. Our study reveals the establishment of preferential interactions between the imidazolium cations of ILs and the guanine bases in the DNA groove that lead to more effective stacking between the guanine bases even at high temperatures. Interestingly, we observe that this trend for ILs sharing the same chloride anion is further enhanced as the alkyl chain on the imidazolium cation gets shorter. The results from the present investigation lead to a more comprehensive view of the IL-mediated interactions with A–T and G–C base pairs during thermal unfolding. [ABSTRACT FROM AUTHOR]

Cytosine plays a preeminent role in DNA methylation, an epigenetic mechanism that regulates gene expression, the misregulation of which can lead to severe diseases. Several methods are nowadays employed for assessing the global DNA methylation levels, but none of them combines simplicity, high sensitivity, and low operating costs to be translated into clinical applications. Ultraviolet (UV) resonant Raman measurements at excitation wavelengths of 272 nm, 260 nm, 250 nm, and 228 nm have been carried out on isolated deoxynucleoside triphosphates (dNTPs), on a dNTP mixture as well as on genomic DNA (gDNA) samples, commercial from salmon sperm and non‐commercial from B16 murine melanoma cell line. The 228 nm excitation wavelength was identified as the most suitable energy for enhancing cytosine signals over the other DNA bases. The UV Raman measurements performed at this excitation wavelength on hyper‐methylated and hypo‐methylated DNA from Jurkat leukemic T‐cell line have revealed significant spectral differences with respect to gDNA isolated from salmon sperm and mouse melanoma B16 cells. This demonstrates how the proper choice of the excitation wavelength, combined with optimized extraction protocols, makes UV Raman spectroscopy a suitable technique for highlighting the chemical modifications undergone by cytosine nucleotides in gDNA upon hyper‐ and hypo‐methylation events. [ABSTRACT FROM AUTHOR]

Laser‐slicing at a diffraction‐limited storage ring light source in the soft X‐ray region is investigated with theoretical and numerical modelling. It turns out that the slicing efficiency is favoured by the ultra‐low beam emittance, and that slicing can be implemented without interference to the standard multi‐bunch operation. Spatial and spectral separation of the sub‐picosecond radiation pulse from a hundreds of picosecond‐long background is achieved by virtue of 1:1 imaging of the radiation source. The spectral separation is enhanced when the radiator is a transverse gradient undulator. The proposed configuration applied to the Elettra 2.0 six‐bend achromatic lattice envisages total slicing efficiency as high as 10−7, one order of magnitude larger than the demonstrated state‐of‐the‐art, at the expense of pulse durations as long as 0.4 ps FWHM and average laser power as high as ∼40 W. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

We present an overview of the FERMI (acronym of Free Electron laser Radiation for Multidisciplinary Investigations) seeded free electron laser (FEL) facility located at the Elettra laboratory in Trieste. FERMI is now in user operation with both the FEL lines FEL-1 and FEL-2, covering the wavelength range between 100 nm and 4 nm. The seeding scheme adopted for photon pulse production makes FERMI unique worldwide and allows the extension of table top laser experiments in the extreme ultraviolet/soft X-ray region. In this paper, we discuss how advances in the performance of the FELs, with respect to coherent control and multi-colour pulse production, may push the development of original experimental strategies to study non-equilibrium behaviour of matter at the attosecond-nanometer time-length scales. This will have a tremendous impact as an experimental tool to investigate a large array of phenomena ranging from nano-dynamics in complex materials to phenomena that are at the heart of the conversion of light into other forms of energy. [ABSTRACT FROM AUTHOR]

Time resolved extreme ultraviolet (EUV) transient reflectivity measurements on non-equilibrium amorphous carbon (a-C) have been carried out by combining optical and free electron laser (FEL) sources. The EUV probing was specifically sensitive to lattice dynamics, since the EUV reflectivity is essentially unaffected by the photo-excited surface plasma. Data have been interpreted in terms of the dynamics of an expanding surface, i.e., a density gradient rapidly forming along the normal surface. This allowed us to determine the characteristic time (τ ... 1 ps) for hydrodynamic expansion in photo-excited a-C. This finding suggests an extremely narrow time window during which the system can be assumed to be in the isochoric regime, a situation that may complicate the study of photo-induced metastable phases of carbon. Data also showed a weak dependence on the probing EUV wavelength, which was used to estimate the electronic temperature (Te ≈ 0.8 eV) of the excited sample. This experimental finding compares fairly well with the results of calculations, while a comparison of our data and calculations with previous transient optical reflectivity measurements highlights the complementarities between optical and EUV probing. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The Diffraction and Projection Imaging (DiProI) beamline at FERMI, the Elettra free-electron laser (FEL), hosts a multi-purpose station that has been opened to users since the end of 2012. This paper describes the core capabilities of the station, designed to make use of the unique features of the FERMI-FEL for performing a wide range of static and dynamic scattering experiments. The various schemes for time-resolved experiments, employing both soft X-ray FEL and seed laser IR radiation are presented by using selected recent results. The ongoing upgrade is adding a reflection geometry setup for scattering experiments, expanding the application fields by providing both high lateral and depth resolution. [ABSTRACT FROM AUTHOR]