Filippo Bencivenga

Two-colour pump–probe experiments with a twin-pulse-seed extreme ultraviolet free-electron laser

Exploring the dynamics of matter driven to extreme non-equilibrium states by an intense ultrashort X-ray pulse is becoming reality, thanks to the advent of free-electron laser technology that allows development of different schemes for probing the response at variable time delay with a second pulse. Here we report the generation of two-colour extreme ultraviolet pulses of controlled wavelengths, intensity and timing by seeding of high-gain harmonic generation free-electron laser with multiple independent laser pulses. The potential of this new scheme is demonstrated by the time evolution of a titanium-grating diffraction pattern, tuning the two coherent pulses to the titanium M-resonance and varying their intensities. This reveals that an intense pulse induces abrupt pattern changes on a time scale shorter than hydrodynamic expansion and ablation. This result exemplifies the essential capabilities of the jitter-free multiple-colour free-electron laser pulse sequences to study evolving states of matter with element sensitivity.

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.

Nanoscale dynamics by short-wavelength four wave mixing experiments

Multi-dimensional spectroscopies with vacuum ultraviolet (VUV)/x-ray free-electron laser (FEL) sources would open up unique capabilities for dynamic studies of matter at the femtosecond?nanometer time?length scales. Using sequences of ultrafast VUV/x-ray pulses tuned to electron transitions enables element-specific studies of charge and energy flow between constituent atoms, which embody the very essence of chemistry and condensed matter physics. A remarkable step forward towards this goal would be achieved by extending the four wave mixing (FWM) approach at VUV/soft x-ray wavelengths, thanks to the use of fully coherent sources, such as seeded FELs. Here, we demonstrate the feasibility of VUV/soft x-ray FWM at Fermi@Elettra and we discuss its applicability to probe ultrafast intramolecular dynamics, charge injection processes involving metal oxides and electron correlation and magnetism in solid materials. The main advantage in using VUV/soft x-ray wavelengths is in adding element-sensitivity to FWM methods by exploiting the core resonances of selected atoms in the sample.

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.

The mixed longitudinal?transverse nature of collective modes in water

We report high-resolution, high-statistics inelastic x-ray scattering measurements of the dynamic structure factor of water as a function of momentum and energy transfer in various thermodynamic conditions, including high-pressure liquid near the melting point, supercooled liquid and polycrystalline ice. For momentum transfer values below 8 nm−1, two collective excitations associated with longitudinal and transverse acoustic modes were observed. Above 8 nm−1, another excitation was detected in the liquid. Comparison with polycrystalline data and molecular dynamics simulations suggests that this mode is related to longitudinal–transverse mixing of mode symmetry.

Temperature and density dependence of the structural relaxation time in water by inelastic ultraviolet scattering

The density and temperature dependence of the structural relaxation time (tau) in water was determined by inelastic ultraviolet scattering spectroscopy in the thermodynamic range (P=1-4000 bars, T=253-323 K), where several water anomalies take place. We observed an activation (Arrhenius) temperature dependence of tau at constant density and a monotonic density decrease at constant temperature. The latter trend was accounted for by introducing a density-dependent activation entropy associated to water local structure. The combined temperature and density behavior of tau indicates that differently from previous results, in the probed thermodynamic range, the relaxation process is ruled by a density-dependent activation Helmholtz free energy rather than a simple activation energy. Finally, the extrapolation of the observed phenomenology at lower temperature suggests a substantial agreement with the liquid-liquid phase transition hypothesis.

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.

Probing matter under extreme conditions at Fermi@Elettra: the TIMEX beamline

FERMI@Elettra is a new free-electron-laser (FEL) facility, presently under commissioning, able to generate subpicosecond photon pulses of high intensity in the far ultraviolet and soft X-ray range (λ=100-20 nm for the present FEL1 source, extended in future to 4 nm with the FEL2 source). Here we briefly describe the present status of the TIMEX end-station, devoted to perform experiments on condensed matter under extreme conditions. The layout of the end-station, presently in the final stages of construction, is reported showing the details of the optics and sample environment. The potential for transmission, reflection, scattering, as well as pump-and-probe experiments is discussed taking into account that FEL pulses can heat thin samples up to the warm dense matter (WDM) regime. The calculated deposited energy in selected elemental films, including saturation effects, shows that homogeneous heating up to very high temperatures (1-10 eV for the electrons) can be easily reached with a suitable tuning of the energy and focus of the soft x-ray pulses of FERMI@Elettra. The results of the first test of the TIMEX end-station are also reported.

Pressure dependence of the large-scale structure of water.

We report on small-angle x-ray scattering measurements on liquid water aimed at characterizing the pressure evolution of its large-scale structure. Diffraction profiles have been fitted assuming a Lorentzian dependence on the exchanged momentum. As a result, we observe an anomalous behavior of the diffracted intensity that tends to disappear, increasing either the pressure or the temperature. This effect is discussed in detail and imputed to the ability of hydrostatic pressure to weaken hydrogen bonds.

Multipurpose end-station for coherent diffraction imaging and scattering at FERMI@Elettra free-electron laser facility

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.