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The electronic excitation occurring on adsorbates at ultrafast time scales from optical lasers that initiate surface chemical reactions is still an open question. Here, we report the ultrafast temporal evolution of X-ray absorption spectroscopy (XAS) and X-ray emission spectroscopy (XES) of a simple well known adsorbate prototype system, namely carbon (C) atoms adsorbed on a nickel (Ni(100)) surface, following intense laser optical pumping at 400 nm. We observe ultrafast (~100 fs) changes in both XAS and XES showing clear signatures of the formation of a hot electron-hole pair distribution on the adsorbate. This is followed by slower changes on a few ps time scale, shown to be consistent with thermalization of the complete C/Ni system. Density functional theory spectrum simulations support this interpretation., 33 pages, 12 figures. Submitted to Physical Review Letters

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 (

International audience; In eukaryotic cells, silent chromatin is mainly found at the nuclear periphery forming subnuclear compartments that favor silencing establishment. Here, we set up an inducible system to monitor silencing establishment at an ectopic locus in relation with its subnuclear localization in budding yeast. We previously showed that introducing LacI bound lacO arrays in proximity to gene flanked by HML silencers favors the recruitment of the yeast silencing complex SIR at this locus, leading to its silencing and anchoring at the nuclear periphery. Using an inducible version of this system, we show that silencing establishment is a stepwise process occurring over several cell cycles, with the progressive recruitment of the SIR complex. In contrast, we observed a rapid, SIR-independent perinuclear anchoring, induced by the high amount of LacI binding at the lacO array leading to nucleosome eviction at this array and to the phosphorylation of H2A in the neighboring nucleosomes by Mec1 kinase. While the initial phosphorylation of H2A (H2A-P) and perinuclear anchoring are independent of the SIR complex, its latter recruitment stabilizes H2A-P and reinforces the perinuclear anchoring. Finally, we showed that Sir3 spreading stabilizes nucleosomes and limits the access of specific DNA-binding protein to DNA.

The Balkan Vegetation Database (BVD; GIVD ID: EU-00-019) is a regional database, which was established in 2014. It comprises phytosociological relevés covering various vegetation types from nine countries of the Balkan Peninsula (Albania – 153 relevés, Bosnia and Herzegovina – 1715, Bulgaria – 12,282, Greece – 465, Croatia – 69, Kosovo – 493, Montenegro – 440, North Macedonia – 13 and Serbia – 2677). Currently, it contains 18,306 relevés (compared to 9.580 in 2016), and most of them (82.8%) are geo-referenced. The database includes both digitized relevés from the literature (65.6%) and unpublished data (34.5%). Plot size is available for 84.7% of all relevés. During the last four years some “header data information” was improved e.g. elevation (now available for 83.4% of all relevés), aspect (67.7%), slope (66%), total cover of vegetation (54.3%), cover of tree, shrub, herb, bryophyte and lichen layers (27.1%, 20.1%, 40.2%, 11.5% and 2.1%), respectively. Data access is either semi-restricted (65.6%) or restricted (34.4%). Most relevés (84.6%) are classified to syntaxa of different levels. The database has been used for numerous studies with various objectives from floristic, vegetation and habitat-related topics, to macroecological studies at the local, regional, national, continental and global levels. During the last four years, BVD data were requested from 111 different projects via the EVA and sPlot databases.

The journal of chemical physics 157(16), 164705 (2022). doi:10.1063/5.0114399, We report on carbon monoxide desorption and oxidation induced by 400 nm femtosecond laser excitation on the O/Ru(0001) surface probed by time-resolved x-ray absorption spectroscopy (TR-XAS) at the carbon K-edge. The experiments were performed under constant background pressures of CO (6 × 10$^{−8}$ Torr) and O$_2$ (3 × 10$^{−8}$ Torr). Under these conditions, we detect two transient CO species with narrow 2$π^*$ peaks, suggesting little 2π* interaction with the surface. Based on polarization measurements, we find that these two species have opposing orientations: (1) CO favoring a more perpendicular orientation and (2) CO favoring a more parallel orientation with respect to the surface. We also directly detect gas-phase CO2 using a mass spectrometer and observe weak signatures of bent adsorbed CO2 at slightly higher x-ray energies than the 2$π^*$ region. These results are compared to previously reported TR-XAS results at the O K-edge, where the CO background pressure was three times lower (2 × 10$^{−8}$ Torr) while maintaining the same O$_2$ pressure. At the lower CO pressure, in the CO 2$π^*$ region, we observed adsorbed CO and a distribution of OC–O bond lengths close to the CO oxidation transition state, with little indication of gas-like CO. The shift toward “gas-like” CO species may be explained by the higher CO exposure, which blocks O adsorption, decreasing O coverage and increasing CO coverage. These effects decrease the CO desorption barrier through dipole–dipole interaction while simultaneously increasing the CO oxidation barrier., Published by American Institute of Physics, Melville, NY

The advent of extreme ultraviolet (EUV) and soft x-ray free electron lasers (FELs) has enabled nonlinear optical experiments at wavelengths shorter than the visible-UV range. An important class of experiments is those based on the four-wave-mixing (FWM) approach, which are often based on interactions between pulses at different wavelengths. The exploitation of multiple EUV/soft x-ray wavelengths is not straightforward, but it can significantly expand the range of applications. In this manuscript we report on an experimental approach, based on the concomitant use of a non-collinear split-delay-and-recombination unit (“mini-Timer”) and on a two-color seeded FEL emission scheme (“twin-seed mode”). We used a diamond sample for demonstrating the capability of this setup of generating and detecting a FWM signal stimulated by two-color EUV FEL pulses. This approach can be further exploited for developing experimental methods based on non-linear EUV/x-ray optics.

Understanding and controlling the thermal transport at nanoscale is a key ingredient for the development of future nanoelectronical devices. In this study of thin silicon carbide (SiC) membrane we demonstrate the potential of free electron laser extreme ultraviolet (EUV) transient grating (TG) technique as contactless probe for thermoelastic response at length scales of 84 nm, where the Fourier heat diffusion law is no longer valid. The results have revealed that the mechanical behavior of the system can be fully described in the framework of Lamb waves. Moreover, by use of a bidimensional spatial detector to measure the TG signal, a new feature is the observed, time dependence in the emission angle of the transient diffraction, correlated to the transient grating signal intensity.

Laser and particle beams 37(2), 235 - 241 (2019). doi:10.1017/S0263034619000326, Modern free-electron lasers (FEL) operating in XUV (extreme ultraviolet) or X-ray range allow an access to novel research areas. An example is the ultrafast ionization of a solid by an intense femtosecond FEL pulse in XUV which consequently leads to a change of the complex index of refraction on an ultrashort timescale. The photoionization and subsequent impact ionization resulting in electronic and atomic dynamics are modeled with our hybrid code XTANT(X-ray thermal and non-thermal transitions) and a Monte Carlo code XCASCADE(X-ray-induced electron cascades). The simulations predict the temporal kinetics of FEL-induced electron cascades and thus yield temporally and spatially resolved information on the induced changes of the optical properties. In a series of experiments at FERMI and LCLS, single shot measurements with spatio-temporal encoding of the ionization process have been performed by a correlation of the FEL pump pulse with an optical femtosecond probe pulse. An excellent agreement between the experiment and the simulation has been found. We also show that such kind of experiments forms the basis for pulse duration and arrival time jitter monitoring as currently under development for XUV-FELs, Published by Cambridge Univ. Press, Cambridge

Physical review letters 127(1), 016802 (2021). doi:10.1103/PhysRevLett.127.016802, We use a pump-probe scheme to measure the time evolution of the C K-edge x-ray absorption spectrum from CO/Ru(0001) after excitation by an ultrashort high-intensity optical laser pulse. Because of the short duration of the x-ray probe pulse and precise control of the pulse delay, the excitation-induced dynamics during the first picosecond after the pump can be resolved with unprecedented time resolution. By comparing with density functional theory spectrum calculations, we find high excitation of the internal stretch and frustrated rotation modes occurring within 200 fs of laser excitation, as well as thermalization of the system in the picosecond regime. The ���100 fs initial excitation of these CO vibrational modes is not readily rationalized by traditional theories of nonadiabatic coupling of adsorbates to metal surfaces, e.g., electronic frictions based on first order electron-phonon coupling or transient population of adsorbate resonances. We suggest that coupling of the adsorbate to nonthermalized electron-hole pairs is responsible for the ultrafast initial excitation of the modes., Published by APS, College Park, Md.

Ultrashort optical pulses can trigger a variety of non-equilibrium processes in magnetic thin films affecting electrons and spins on femtosecond timescales. In order to probe the charge and magnetic degrees of freedom simultaneously, we developed an X-ray streaking technique that has the advantage of providing a jitter-free picture of absorption cross-section changes. In this paper, we present an experiment based on this approach, which we performed using five photon probing energies at the Ni M2,3-edges. This allowed us to retrieve the absorption and magnetic circular dichroism time traces, yielding detailed information on transient modifications of electron and spin populations close to the Fermi level. Our findings suggest that the observed absorption and magnetic circular dichroism dynamics both depend on the extreme ultraviolet (XUV) probing wavelength, and can be described, at least qualitatively, by assuming ultrafast energy shifts of the electronic and magnetic elemental absorption resonances, as reported in recent work. However, our analysis also hints at more complex changes, highlighting the need for further experimental and theoretical studies in order to gain a thorough understanding of the interplay of electronic and spin degrees of freedom in optically excited magnetic thin films.

The development of ultra-bright extreme ultraviolet (EUV) and X-ray free electron laser (FEL) sources has enabled the extension of wave-mixing approaches into the short wavelength regime. Such a class of experiments relies upon nonlinear interactions among multiple light pulses offering a unique tool for exploring the dynamics of ultrafast processes and correlations between selected excitations at relevant length and time scales adding elemental and site selectivity as well. Besides the availability of a suitable photon source, the implementation of wave mixing methodology requires efforts in developing the instrumental set-up. We have realized at the FERMI FEL two dedicated set-ups to handle multiple FEL beams with preselected parameters in a non-collinear fashion and control their interaction sequence at the target. These unique apparatuses, combined with the exceptional characteristics of the seeded FERMI FEL, have allowed us to make the first steps into this field and further advances are foreseen in the near future.

We use time-resolved x-ray resonant magnetic scattering (TR-XRMS) at the Co ${M}_{2,3}$ and Tb ${O}_{1}$ edges to study ultrafast demagnetization in an amorphous ${\mathrm{Co}}_{88}{\mathrm{Tb}}_{12}$ alloy with stripe domains. Combining the femtosecond temporal with nanometer spatial resolution of our experiment, we demonstrate that the equilibrium spin texture of the thin film remains unaltered by the optical pump pulse on ultrashort timescales ($l1\phantom{\rule{0.28em}{0ex}}\mathrm{ps}$). However, after $\ensuremath{\simeq}4$ ps, we observe the onset of a significant domain wall broadening, which we attribute to a reduction of the uniaxial magnetic anisotropy of the system, due to energy transfer to the lattice. Static temperature-dependent magnetometry measurements combined with analytical modeling of the magnetic structure of the thin film corroborate this interpretation.

We present the development of a high-power laser source operating at 532 nm produced by frequency doubling a Ybdoped fiber amplifier. The fiber amplifier has a multistage design, and uses large mode area Yb-doped fibers as the gain medium to produce > 2 kW of laser power at 1064 nm. The amplifier design is optimized to reduce non-linear effects, and operates at linewidths as narrow as 45 GHz. By focusing the fiber amplifier output into an LBO crystal, more than 1 kW of 532 nm light is produced. Single pass conversion efficiencies as high as 54% are achieved providing a unique combination of high power and high quality 532 nm laser source. The 532 nm laser is fiber coupled, making it an ideal source for industrial applications.

The recent development of ultrafast extreme ultraviolet (XUV) coherent light sources bears great potential for a better understanding of the structure and dynamics of matter. Promising routes are advanced coherent control and nonlinear spectroscopy schemes in the XUV energy range, yielding unprecedented spatial and temporal resolution. However, their implementation has been hampered by the experimental challenge of generating XUV pulse sequences with precisely controlled timing and phase properties. In particular, direct control and manipulation of the phase of individual pulses within an XUV pulse sequence opens exciting possibilities for coherent control and multidimensional spectroscopy, but has not been accomplished. Here, we overcome these constraints in a highly time-stabilized and phase-modulated XUV-pump, XUV-probe experiment, which directly probes the evolution and dephasing of an inner subshell electronic coherence. This approach, avoiding any XUV optics for direct pulse manipulation, opens up extensive applications of advanced nonlinear optics and spectroscopy at XUV wavelengths., Light pulses with controllable parameters are desired for studying the fundamental properties of matter. Here the authors generate and use phase-manipulated and highly time-stable XUV pulse pairs to probe the coherent evolution and dephasing of XUV electronic coherences in helium and argon.

We demonstrate an all-optical approach for measuring spectrograms of individual FEL pulses by measuring a spectrally-resolved EUV-EUV-optical four-wave-mixing signal. We experimentally demonstrate that this is phase-sensitive can be applied to structured and unstable pulse trains.

The transient dynamics of carbon monoxide (CO) molecules on a Ru(0001) surface following femtosecond optical laser pump excitation has been studied by monitoring changes in the unoccupied electronic structure using an ultrafast X-ray free-electron laser (FEL) probe. The particular symmetry of perpendicularly chemisorbed CO on the surface is exploited to investigate how the molecular orientation changes with time by varying the polarization of the FEL pulses. The time evolution of spectral features corresponding to the desorption precursor state was well distinguished due to the narrow line-width of the C K-edge in the X-ray absorption (XA) spectrum, illustrating that CO molecules in the precursor state rotated freely and resided on the surface for several picoseconds. Most of the CO molecules trapped in the precursor state ultimately cooled back down to the chemisorbed state, while we estimate that similar to 14.5 +/- 4.9% of the molecules in the precursor state desorbed into the gas phase. It was also observed that chemisorbed CO molecules diffused over the metal surface from on-top sites toward highly coordinated sites. In addition, a new "vibrationally hot precursor" state was identified in the polarization-dependent XA spectra.

The rapid development of extreme ultraviolet (EUV) and x-ray ultrafast coherent light sources such as free electron lasers (FELs) has triggered the extension of wave-mixing techniques to short wavelengths. This class of experiments, based on the interaction of matter with multiple light pulses through the Nth order susceptibility, holds the promise of combining intrinsic ultrafast time resolution and background-free signal detection with nanometer spatial resolution and chemical specificity. A successful approach in this direction has been the combination of the unique characteristics of the seeded FEL FERMI with dedicated four-wave-mixing (FWM) setups, which leads to the demonstration of EUV-based transient grating (TG) spectroscopy. In this perspective paper, we discuss how the TG approach can be extended toward more general FWM spectroscopies by exploring the intrinsic multiparameter nature of nonlinear processes, which derives from the ability of controlling the properties of each field independently.

This theoretical overview aims to analyze the law provisions given in the Electronic Identity Act. The overview also regards the process of gradual transition towards e-Justice within the context of the Bulgarian egovernment.

We present the design of a Cr:forsterite based single-frequency master-oscillator power-amplifier laser system delivering much higher output energy compared to previous literature reports. The system has four amplifying stages with two-pass configuration each, thus enabling the generation of 24 mJ output energy in the spectral region around 1262 nm. It is demonstrated that the presented Cr:forsterite amplifier preserves high spectral and pulse quality, allowing a straightforward energy scaling. This laser system is a promising tool for tunable nonlinear down-conversion to the mid-infrared spectral range and will be a key building block in a system for high-resolution muonic hydrogen spectroscopy in the 6.8 μm range.

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. Echo-enabled harmonic generation in a free-electron laser enables 45th harmonic pulses from a 264 nm wavelength seed, yielding 5.9 nm wavelength coherent output.

Recent advances in ultrafast extreme ultraviolet (EUV) and x-ray light sources provide direct access to fundamental time and length scales for biology, chemistry, and materials physics. However, such light pulses are challenging to measure due to the need for femtosecond time resolution at difficult-to-detect wavelengths. Also, single-shot measurements are needed because severe pulse-to-pulse fluctuations are common. Here we demonstrate single-shot, complete field measurements by applying a novel version of frequency resolved optical gating. An EUV free electron laser beam creates a transient grating containing the pulse’s electric field information, which is read out with a 400 nm probe pulse. By varying the time delay between two copies of the EUV pump, rather than between the pump and the probe, we separate the needed coherent wave mixing from the slow incoherent response. Because this approach uses photoionization, it should be applicable from the vacuum ultraviolet to hard x rays.

The Balkan Vegetation Database (BVD; GIVD ID: EU-00-019; http://www.givd.info/ID/EU-00- 019) is a regional database that consists of phytosociological relevés from different vegetation types from six countries on the Balkan Peninsula (Albania, Bosnia and Herzegovina, Bulgaria, Kosovo, Montenegro and Serbia). Currently, it contains 9,580 relevés, and most of them (78%) are geo-referenced. The database includes digitized relevés from the literature (79%) and unpublished data (21%). Herein we present descriptive statistics about attributive relevé information. We developed rules that regulate governance of the database, data provision, types of data availability regimes, data requests and terms of use, authorships and relationships with other databases. The database offers an extensive overview about studies on the local, regional and SE European levels including information about flora, vegetation and habitats.

The first one-step synthesis of dumbbell-like gold–iron oxide nanoparticles has been reported here. Surface functionalization with a biocompatible chitosan matrix allowed us to obtain a novel targetable diagnostic and therapeutic tool.

We report on a laser system based on difference frequency generation (DFG) to produce tunable, narrow-linewidth ( < 30 p m ), and comparatively high-energy mid-IR radiation in the 6.8 µm region. The system exploits a lithium thioindate ( L i I n S 2 ) nonlinear crystal and nanosecond pulses generated by single-frequency Nd:YAG and Cr:forsterite lasers at 1064 and 1262 nm, respectively. Two experimental configurations are used: in the first one, single-pass, the mid-IR energy achieved is 205 µJ. Additional increments, up to 540 µJ, are obtained by performing double-pass through the nonlinear crystal. This laser has been developed for high-resolution photon-hungry spectroscopy in the mid-IR.

We hereby report on a set of transient optical reflectivity and transmissivity measurements performed on silicon nitride thin membranes excited by extreme ultraviolet (EUV) radiation from a free electron laser (FEL). Experimental data were acquired as a function of the membrane thickness, FEL fluence and probe polarization. The time dependence of the refractive index, retrieved using Jones matrix formalism, encodes the dynamics of electron and lattice excitation following the FEL interaction. The observed dynamics are interpreted in the framework of a two temperature model, which permits to extract the relevant time scales and magnitudes of the processes. We also found that in order to explain the experimental data thermo-optical effects and inter-band filling must be phenomenologically added to the model.

Experimental approaches based on nonlinear optical processes (wave-mixing) have allowed major breakthroughs in diverse fields of science and technology. Nevertheless, these concepts were restricted to the optical regime due to the lack of coherent photon sources of sufficient peak brightness at sub-optical wavelengths. Nowadays, while the development of free electron lasers (FELs) potentially allows extreme ultraviolet (EUV) and X-ray wave-mixing, their full exploitation still requires efforts in instrumentation developments. The need to control (both in the spatial and temporal coordinates) multiple FEL input pulses, which may have different photon frequencies and polarizations, calls for the developments of instruments with a higher degree of complexity with respect to those typically used at synchrotron and FEL beamlines. Here we report on the progresses in the development of such kind of instrumentation at the FERMI FEL facility. Our FEL-based wave-mixing setups rely upon the transient grating (TG) approach, which represents a relevant benchmark for the development of advanced EUV/soft x-ray four-wave-mixing (FWM) experiments, as for instance coherent Raman scattering and multi-dimensional spectroscopy. © 2018 Elsevier B.V.

Ultrafast dynamics are generally investigated using stroboscopic pump-probe measurements, which characterize the sample properties for a single, specific time delay. These measurements are then repeated for a series of discrete time delays to reconstruct the overall time trace of the process. As a consequence, this approach is limited to the investigation of fully reversible phenomena. We recently introduced an off-axis zone plate based X-ray streaking technique, which overcomes this limitation by sampling the relaxation dynamics with a single femtosecond X-ray pulse streaked over a picosecond long time window. In this article we show that the X-ray absorption cross section can be employed as the contrast mechanism in this novel technique. We show that changes of the absorption cross section on the percent level can be resolved with this method. To this end we measure the ultrafast magnetization dynamics in CoDy alloy films. Investigating different chemical compositions and infrared pump fluences, we demonstrate the routine applicability of this technique. Probing in transmission the average magnetization dynamics of the entire film, our experimental findings indicate that the demagnetization time is independent of the specific infrared laser pump fluence. These results pave the way for the investigation of irreversible phenomena in a wide variety of scientific areas., Comment: 9 pages, 5 figures

We investigate the excitation of coherent acoustic and optical phonons by ultrashort extreme ultraviolet (EUV) pulses produced by a free electron laser. Two crossed femtosecond EUV (wavelength 12.7 nm) pulses are used to excite coherent phonons at a wavelength of 280 nm, which are detected via diffraction of an optical probe beam. Longitudinal and surface acoustic waves are measured in BK-7 glass, diamond, and Bi4Ge3O12; in the latter material, the excitation of a coherent optical phonon mode is also observed. We discuss probing different acoustic modes in reflection and transmission geometries and frequency mixing of surface and bulk acoustic waves in the signal. The use of extreme ultraviolet radiation will allow the creation of tunable GHz to THz acoustic sources in any material without the need to fabricate transducer structures. The contribution by the MIT group was supported by the U.S. Department of Energy, Office of Basic Energy Sciences under Award No. DE-FG02-00ER15087. The JILA group graciously acknowledges support from the Department of Energy BES Award No. DE-FG02-99ER14982 and the Gordon and Betty Moore Foundation's EPiQS Initiative through Grant No. GBMF: 4538, and J.K. acknowledges support from an SRC Fellowship. The Elettra group acknowledges the European Research Council Grant No. 202804-TIMER. A.C. and T.F. acknowledge the Swiss NSF through the NCCR-MUST.

We propose and study the use of a single-shot, collinear, tilted-front cross-correlator scheme for relative pulse timing measurements. In a very simple geometry, sub-0.5-fs resolution and larger than 3-ps instantaneous time window in relative pulse timing measurement are demonstrated. In addition, the scheme is shown to be practically immune to the changes of the energy of the monitored pulses exceeding 10 %. On the basis of the obtained results, the scheme can be expected to find applications in diagnostics and stabilization of timing jitter and drifts of pulses originating from different sources.

Four-wave mixing processes are achieved at suboptical wavelengths by using a free-electron laser as a source to generate extreme ultraviolet pulses that produce transient gratings. The phenomenon of four-wave mixing (FWM) occurs when two wavelengths of light interact to produce two extra wavelengths in the signal. It has been exploited in many optics technologies, from optical fibre communication to spectroscopy. Until now FWM has been limited to optical wavelengths. Here Filippo Bencivenga et al. show how to stimulate four-wave mixing processes at suboptical wavelengths using the FERMI free-electron laser as a source to generate extreme ultraviolet pulses that produce transient gratings. The extension of FWM to shorter wavelengths — combined with new developments in free-electron lasers — promises higher resolution for many techniques and the possibility of probe excitations to higher energies. Four-wave mixing (FWM) processes, based on third-order nonlinear light–matter interactions, can combine ultrafast time resolution with energy and wavevector selectivity, and enable the exploration of dynamics inaccessible by linear methods1,2,3,4,5,6,7. The coherent and multi-wave nature of the FWM approach has been crucial in the development of advanced technologies, such as silicon photonics8, subwavelength imaging9 and quantum communications10. All these technologies operate at optical wavelengths, which limits the spatial resolution and does not allow the probing of excitations with energy in the electronvolt range. Extension to shorter wavelengths—that is, the extreme ultraviolet and soft-X-ray ranges—would allow the spatial resolution to be improved and the excitation energy range to be expanded, as well as enabling elemental selectivity to be achieved by exploiting core resonances5,6,7,11,12,13,14. So far, FWM applications at such wavelengths have been prevented by the absence of coherent sources of sufficient brightness and of suitable experimental set-ups. Here we show how transient gratings, generated by the interference of coherent extreme-ultraviolet pulses delivered by the FERMI free-electron laser15, can be used to stimulate FWM processes at suboptical wavelengths. Furthermore, we have demonstrated the possibility of observing the time evolution of the FWM signal, which shows the dynamics of coherent excitations as molecular vibrations. This result opens the way to FWM with nanometre spatial resolution and elemental selectivity, which, for example, would enable the investigation of charge-transfer dynamics5,6,7. The theoretical possibility of realizing these applications has already stimulated ongoing developments of free-electron lasers16,17,18,19,20: our results show that FWM at suboptical wavelengths is feasible, and we hope that they will enable advances in present and future photon sources.

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.A description of the novel timing methodologies developed at the FERMI FEL facility is given.

It was shown recently that the Fe magnetization reversal in the Fe/MnAs/GaAs(001) epitaxial system, attained by temperature control of the regular stripe pattern of the MnAs ?- and ?-phases, can also be driven by an ultrashort optical laser pulse. In the present time-resolved scattering experiment, we address the dynamics of the MnAs ?/? self-organized stripe pattern induced by a 100 fs optical laser pulse, using as a probe the XUV radiation from the FERMI free-electron laser. We observe a loss in the diffraction intensity from the ordered ?/? stripes that occurs at two characteristic timescales in the range of ~10-12 and ~10-10 s. We associate the first intensity drop with ultrafast electron-lattice energy exchange processes within the laser-MnAs interaction volume and the second with thermal diffusion towards the MnAs/GaAs interface. With the support of model calculations, the observed dynamics are interpreted in terms of the formation of a laterally homogeneous MnAs overlayer, the thickness of which evolves in time, correlating the MnAs microstructure dynamics with the Fe magnetization response.

The potential of the two-color mode implemented at the FERMI free-electron laser (FEL) source for pumping and probing selectively different atomic species has been demonstrated by time-resolved scattering experiments with permalloy (FeNi alloy) and NiFe 2 O 4 samples. We monitored the ultra-fast demagnetization of Ni induced by the pump FEL pulse, by tuning the linearly-polarized FEL probe pulse to the Ni-3p resonance and measuring the scattered intensity in the transverse magneto-optical Kerr effect geometry. The measurements were performed by varying the intensity of the FEL pump pulse, tuning its wavelength to and off of the Fe-3p resonance, and by spanning the FEL probe pulse delays across the 300–900 fs range. The obtained results have Photonics 2017, 4, 6 2 of 10 evidenced that for the case of NiFe 2 O 4 , there is a sensible difference in the magnetic response at the Ni site when the pump pulse causes electronic excitations at the Fe site.

The talk describes the status, recent progress and near future plans in the Free Electron Laser seeding by ultrashort UV pulses implemented at FERMI as a root to generate XUV pulses with very exciting properties.

The development of free electron laser (FEL) sources has provided an unprecedented bridge between the scientific communities working with ultrafast lasers and extreme ultraviolet (XUV) and X-ray radiation. Indeed, in recent years an increasing number of FEL-based applications have exploited methods and concepts typical of advanced optical approaches. In this context, we recently used a seeded FEL to demonstrate a four-wave-mixing (FWM) process stimulated by coherent XUV radiation, namely the XUV transient grating (X-TG). We hereby report on X-TG measurements carried out on a sample of silicon nitride (Si3N4). The recorded data bears evidence for two distinct signal decay mechanisms: one occurring on a sub-ps timescale and one following slower dynamics extending throughout and beyond the probed timescale range (100 ps). The latter is compatible with a slower relaxation (time decay > ns), that may be interpreted as the signature of thermal diffusion modes. From the peak intensity of the X-TG signal we could estimate a value of the effective third-order susceptibility which is substantially larger than that found in SiO2, so far the only sample with available X-TG data. Furthermore, the intensity of the time-coincidence peak shows a linear dependence on the intensity of the three input beams, indicating that the measurements were performed in the weak field regime. However, the timescale of the ultrafast relaxation exhibits a dependence on the intensity of the XUV radiation. We interpreted the observed behaviour as the generation of a population grating of free-electrons and holes that, on the sub-ps timescale, relaxes to generate lattice excitations. The background free detection inherent to the X-TG approach allowed the determination of FEL-induced electron dynamics with a sensitivity largely exceeding that of transient reflectivity and transmissivity measurements, usually employed for this purpose. This journal is © The Royal Society of Chemistry.

Stefania Biffi,1 Luca Petrizza,2 Chiara Garrovo,1 Enrico Rampazzo,2 Laura Andolfi,3 Pierangela Giustetto,4 Ivaylo Nikolov,5 Gabor Kurdi,5 Miltcho Boyanov Danailov,5 Giorgio Zauli,1 Paola Secchiero,6 Luca Prodi2 1Institute for Maternal and Child Health – IRCCS “Burlo Garofolo”, Trieste, 2Department of Chemistry ‘‘G Ciamician’’, University of Bologna, Bologna, 3IOM-CNR TASC Laboratory, Basovizza, Trieste, 4Ephoran – Multi-Imaging Solutions, Bioindustry Park Silvano Fumero, Torino, 5Elettra-Sincrotrone Trieste, Trieste, 6Department of Morphology, Surgery and Experimental Medicine and LTTA Centre, University of Ferrara, Ferrara, Italy Purpose: The aim of the present study was to develop nanoprobes with theranostic features, including – at the same time – photoacoustic, near-infrared (NIR) optical imaging, and photothermal properties, in a versatile and stable core–shell silica-polyethylene glycol (PEG) nanoparticle architecture. Materials and methods: We synthesized core–shell silica-PEG nanoparticles by a one-pot direct micelles approach. Fluorescence emission and photoacoustic and photothermal properties were obtained at the same time by appropriate doping with triethoxysilane-derivatized cyanine 5.5 (Cy5.5) and cyanine 7 (Cy7) dyes. The performances of these nanoprobes were measured in vitro, using nanoparticle suspensions in phosphate-buffered saline and blood, dedicated phantoms, and after incubation with MDA-MB-231 cells. Results: We obtained core–shell silica-PEG nanoparticles endowed with very high colloidal stability in water and in biological environment, with absorption and fluorescence emission in the NIR field. The presence of Cy5.5 and Cy7 dyes made it possible to reach a more reproducible and higher doping regime, producing fluorescence emission at a single excitation wavelength in two different channels, owing to the energy transfer processes within the nanoparticle. The nanoarchitecture and the presence of both Cy5.5 and Cy7 dyes provided a favorable agreement between fluorescence emission and quenching, to achieve optical imaging and photoacoustic and photothermal properties. Conclusion: We obtained rationally designed nanoparticles with outstanding stability in biological environment. At appropriate doping regimes, the presence of Cy5.5 and Cy7 dyes allowed us to tune fluorescence emission in the NIR for optical imaging and to exploit quenching processes for photoacoustic and photothermal capabilities. These nanostructures are promising in vivo theranostic tools for the near future. Keywords: dye-doped nanoparticles, optical imaging, NIR imaging, photoacoustic imaging, photothermal therapy, PEGylated nanoparticles

Free-electron lasers (FELs) are promising devices for generating light with laser-like properties in the extreme ultraviolet and X-ray spectral regions. Recently, FELs based on the self-amplified spontaneous emission (SASE) mechanism have allowed major breakthroughs in diffraction and spectroscopy applications, despite the relatively large shot-to-shot intensity and photon-energy fluctuations and the limited longitudinal coherence inherent in the SASE mechanism. Here, we report results on the initial performance of the FERMI seeded FEL, based on the high-gain harmonic generation configuration, in which an external laser is used to initiate the emission process. Emission from the FERMI FEL-1 source occurs in the form of pulses carrying energy of several tens of microjoules per pulse and tunable throughout the 65 to 20 nm wavelength range, with unprecedented shot-to-shot wavelength stability, low-intensity fluctuations, close to transform-limited bandwidth, transverse and longitudinal coherence and full control of polarization.

Base excision repair (BER) removes DNA damage induced by endogenous reactive oxygen species or ionizing radiation, important breast cancer risk factors. Genetic variation associated with impaired BER might thus increase breast cancer risk. Therefore, we assessed risk associations of 123 common single nucleotide polymorphisms (SNPs) in 19 BER genes in 1,639 postmenopausal breast cancer cases and 1,967 controls from the German population-based case-control study MARIE. SNPs were tagging SNPs representing genetic variation across the gene together with potentially functional SNPs. Risk associations were assessed using conditional logistic regression, adjusted for potential breast cancer risk factors. Significant associations between polymorphisms and breast cancer risk were found for one SNP in PARP2 and three SNPs in the mitochondrial DNA polymerase gamma, POLG. A SNP in the promoter region of POLG (rs2856268, A>G) showed a protective effect for homozygous GG carriers (odds ratio 0.81, 95% confidence intervals 0.65–1.00). Joint analysis of an enlarged sample set and haplotype analysis supported the results for POLG. Quantification of POLG mRNA expression in lymphocytes of 148 breast cancer patients revealed higher mRNA levels for rs2856268 GG carriers (p value = 0.038). A luciferase promoter assay showed significant differences between constructs harboring the respective alleles. Taken together, our results suggest that genetic variation in the POLG promoter region affects DNA polymerase gamma levels in mitochondria. This could contribute to the reported increase in mitochondrial mutation frequency resulting in dysfunction and altered breast cancer risk. Risk effects and the functional impact of the POLG promoter variant require further confirmation.

A large mode area photonic crystal fiber (LMA PCF) with an effective area of 180 μm 2 is used to generate a high energy, micro-joule range, flat, octave spanning supercontinuum (SC) extending from ~ 600 nm to ~ 1720 nm. A train of femtosecond pulses from a widely-tunable parametric amplifier pumped by a Ti:Sapphire regenerative amplifier system are coupled into a 20 cm length of LMA PCF generating a SC of 1.4 μJ energy. We present an experimental study of the high energy SC as a function of the input power and the pumping wavelength. The spectrum obtained at a pump wavelength of 1260 nm presents spectral flatness variation less than 12 dB over more than 1.1 octave bandwidth. The physical processes behind the SC formation are described in the normal and the anomalous dispersion regions. Our experimental results are successfully compared with the numerical solution of the nonlinear Schrodinger equation.

In this manuscript we report on a compact experimental set-up (“mini-TIMER”) conceived for transient grating (TG) experiments based on free electron laser (FEL) radiation. This set-up has been tested at the seeded FEL facility FERMI (Elettra, Trieste, Italy) and allowed us to observe the first FEL-stimulated TG signal. This experimental result is of the greatest relevance in the context of developing coherent non-linear optical methods into the extreme ultraviolet (EUV) and soft X-ray (SXR) range. Such a challenging task will be addressed in the next future at FERMI by using the present set-up and the forthcoming EIS-TIMER beamline, which is being installed at FERMI and will start the commissioning phase in the second semester 2015. The possibility to use TGs generated by FEL radiation at sub-optical wavelengths would allow developing EUV/SXR four-wave-mixing (FWM) applications, so far considered only theoretically and widely believed to be potentially able to provide major breakthroughs in several fields of science.