Element- and enantiomer-selective visualization of molecular motion in real-time.

Ultrafast optical-domain spectroscopies allow to monitor in real time the motion of nuclei in molecules. Achieving element-selectivity had to await the advent of time resolved X-ray spectroscopy, which is now commonly carried at X-ray free electron lasers. However, detecting light element that are commonly encountered in organic molecules, remained elusive due to the need to work under vacuum. Here, we present an impulsive stimulated Raman scattering (ISRS) pump/carbon K-edge absorption probe investigation, which allowed observation of the low-frequency vibrational modes involving specific selected carbon atoms in the Ibuprofen RS dimer. Remarkably, by controlling the probe light polarization we can preferentially access the enantiomer of the dimer to which the carbon atoms belong.

Extreme ultraviolet transient gratings: A tool for nanoscale photoacoustics.

Collective lattice dynamics determine essential aspects of condensed matter, such as elastic and thermal properties. These exhibit strong dependence on the length-scale, reflecting the marked wavevector dependence of lattice excitations. The extreme ultraviolet transient grating (EUV TG) approach has demonstrated the potential of accessing a wavevector range corresponding to the 10s of nm length-scale, representing a spatial scale of the highest relevance for fundamental physics and forefront technology, previously inaccessible by optical TG and other inelastic scattering methods. In this manuscript we report on the capabilities of this technique in the context of probing thermoelastic properties of matter, both in the bulk and at the surface, as well as discussing future developments and practical considerations.

Atomic and Electronic Structure of Solid-Density Liquid Carbon.

A liquid carbon (l-C) sample is generated through constant volume heating exposing an amorphous carbon foil to an intense ultrashort laser pulse. Time-resolved x-ray absorption spectroscopy at the C K edge is used to monitor the dynamics of the melting process revealing a subpicosecond rearrangement of the electronic structure associated with a sudden change of the C bonding hybridization. The obtained l-C sample, resulting from a nonthermal melting mechanism, reaches a transient equilibrium condition with a temperature of about 14 200 K and pressure in the order of 0.5 Mbar in about 0.3 ps, prior to hydrodynamic expansion. A detailed analysis of the atomic and electronic structure in solid-density l-C based on time-resolved x-ray absorption spectroscopy and theoretical simulations is presented. The method can be fruitfully used for extending the experimental investigation of the C phase diagram in a vast unexplored region covering the 10^{3}-10^{4} K temperature range with pressures up to 1 Mbar.

Ultrafast Plasmon Dynamics in Crystalline LiF Triggered by Intense Extreme UV Pulses.

An extreme ultraviolet pump and visible-light probe transmission experiment in crystalline LiF, carried out at the Free Electron Laser facility FERMI, revealed an oscillating time dependence of the plasmon mode excited in the high-density high-temperature electron plasma. The effect is interpreted as a fingerprint of the electron-ion interaction: the ion motion, shaped by the electron dynamic screening, induces, in turn, electron density fluctuations that cause the oscillation of the plasmon frequency at the timescale of the ion dynamics. Fitting the high resolution transmission data with an RPA model for the temperature-dependent dielectric function, which includes electron self-energy and electron-ion coupling, confirms the interpretation of the time modulation of the plasmon mode.

Exploring the multiparameter nature of EUV-visible wave mixing at the FERMI FEL.

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.

Nanoscale transient gratings excited and probed by extreme ultraviolet femtosecond pulses.

Advances in developing ultrafast coherent sources operating at extreme ultraviolet (EUV) and x-ray wavelengths allow the extension of nonlinear optical techniques to shorter wavelengths. Here, we describe EUV transient grating spectroscopy, in which two crossed femtosecond EUV pulses produce spatially periodic nanoscale excitations in the sample and their dynamics is probed via diffraction of a third time-delayed EUV pulse. The use of radiation with wavelengths down to 13.3 nm allowed us to produce transient gratings with periods as short as 28 nm and observe thermal and coherent phonon dynamics in crystalline silicon and amorphous silicon nitride. This approach allows measurements of thermal transport on the ~10-nm scale, where the two samples show different heat transport regimes, and can be applied to study other phenomena showing nontrivial behaviors at the nanoscale, such as structural relaxations in complex liquids and ultrafast magnetic dynamics.

First Evidence of Purely Extreme-Ultraviolet Four-Wave Mixing.

The extension of nonlinear optical techniques to the extreme-ultraviolet (EUV), soft and hard x-ray regime represents one of the open challenges of modern science since it would combine chemical specificity with background-free detection and ultrafast time resolution. We report on the first observation of a four-wave-mixing (FWM) response from solid-state samples stimulated exclusively by EUV pulses. The all-EUV FWM signal was generated by the diffraction of high-order harmonics of the FERMI free-electron laser (FEL) from the standing wave resulting from the interference of two crossed FEL pulses at the fundamental wavelength. From the intensity of the FWM signal, we are able to extract the first-ever estimate of an effective value of ∼6×10^{-24} m^{2} V^{-2} for the third-order nonlinear susceptibility in the EUV regime. This proof of principle experiment represents a significant advance in the field of nonlinear optics and sets the starting point for a manifold of techniques, including frequency and phase-resolved FWM methods, that are unprecedented in this photon-energy regime.

Optical constants modelling in silicon nitride membrane transiently excited by EUV radiation.

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.

Soft X-Ray Second Harmonic Generation as an Interfacial Probe.

Nonlinear optical processes at soft x-ray wavelengths have remained largely unexplored due to the lack of available light sources with the requisite intensity and coherence. Here we report the observation of soft x-ray second harmonic generation near the carbon K edge (∼284 eV) in graphite thin films generated by high intensity, coherent soft x-ray pulses at the FERMI free electron laser. Our experimental results and accompanying first-principles theoretical analysis highlight the effect of resonant enhancement above the carbon K edge and show the technique to be interfacially sensitive in a centrosymmetric sample with second harmonic intensity arising primarily from the first atomic layer at the open surface. This technique and the associated theoretical framework demonstrate the ability to selectively probe interfaces, including those that are buried, with elemental specificity, providing a new tool for a range of scientific problems.

Characterization of ultrafast free-electron laser pulses using extreme-ultraviolet transient gratings.

The characterization of the time structure of ultrafast photon pulses in the extreme-ultraviolet (EUV) and soft X-ray spectral ranges is of high relevance for a number of scientific applications and photon diagnostics. Such measurements can be performed following different strategies and often require large setups and rather high pulse energies. Here, high-quality measurements carried out by exploiting the transient grating process, i.e. a third-order non-linear process sensitive to the time-overlap between two crossed EUV pulses, is reported. From such measurements it is possible to obtain information on both the second-order intensity autocorrelation function and on the coherence length of the pulses. It was found that the pulse energy density needed to carry out such measurements on solid state samples can be as low as a few mJ cm-2. Furthermore, the possibility to control the arrival time of the crossed pulses independently might permit the development of a number of coherent spectroscopies in the EUV and soft X-ray regime, such as, for example, photon echo and two-dimensional spectroscopy.

Perspective: A toolbox for protein structure determination in physiological environment through oriented, 2D ordered, site specific immobilization.

Revealing the structure of complex biological macromolecules, such as proteins, is an essential step for understanding the chemical mechanisms that determine the diversity of their functions. Synchrotron based X-ray crystallography and cryo-electron microscopy have made major contributions in determining thousands of protein structures even from micro-sized crystals. They suffer from some limitations that have not been overcome, such as radiation damage, the natural inability to crystallize a number of proteins, and experimental conditions for structure determination that are incompatible with the physiological environment. Today, the ultra-short and ultra-bright pulses of X-ray free-electron lasers have made attainable the dream to determine protein structures before radiation damage starts to destroy the samples. However, the signal-to-noise ratio remains a great challenge to obtain usable diffraction patterns from a single protein molecule. With the perspective to overcome these challenges, we describe here a new methodology that has the potential to overcome the signal-to-noise-ratio and protein crystallization limits. Using a multidisciplinary approach, we propose to create ordered, two dimensional protein arrays with defined orientation attached on a self-assembled-monolayer. We develop a literature-based flexible toolbox capable of assembling different kinds of proteins on a functionalized surface and consider using a graphene cover layer that will allow performing experiments with proteins in physiological conditions.

Extreme ultraviolet resonant inelastic X-ray scattering (RIXS) at a seeded free-electron laser.

In the past few years, we have been witnessing an increased interest for studying materials properties under non-equilibrium conditions. Several well established spectroscopies for experiments in the energy domain have been successfully adapted to the time domain with sub-picosecond time resolution. Here we show the realization of high resolution resonant inelastic X-ray scattering (RIXS) with a stable ultrashort X-ray source such as an externally seeded free electron laser (FEL). We have designed and constructed a RIXS experimental endstation that allowed us to successfully measure the d-d excitations in KCoF3 single crystals at the cobalt M2,3-edge at FERMI FEL (Elettra-Sincrotrone Trieste, Italy). The FEL-RIXS spectra show an excellent agreement with the ones obtained from the same samples at the MERIXS endstation of the MERLIN beamline at the Advanced Light Source storage ring (Berkeley, USA). We established experimental protocols for performing time resolved RIXS experiments at a FEL source to avoid X ray-induced sample damage, while retaining comparable acquisition time to the synchrotron based measurements. Finally, we measured and modelled the influence of the FEL mixed electromagnetic modes, also present in externally seeded FELs, and the beam transport with ~120 meV experimental resolution achieved in the presented RIXS setup.

Four-wave-mixing experiments with seeded free electron lasers.

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.

Free electron laser-driven ultrafast rearrangement of the electronic structure in Ti.

High-energy density extreme ultraviolet radiation delivered by the FERMI seeded free-electron laser has been used to create an exotic nonequilibrium state of matter in a titanium sample characterized by a highly excited electron subsystem at temperatures in excess of 10 eV and a cold solid-density ion lattice. The obtained transient state has been investigated through ultrafast absorption spectroscopy across the Ti M2,3-edge revealing a drastic rearrangement of the sample electronic structure around the Fermi level occurring on a time scale of about 100 fs.

Role of the ionization potential in nonequilibrium metals driven to absorption saturation.

A composite metallic foil (Al/Mg/Al) has been exposed to intense sub-100 fs free electron laser (FEL) pulses and driven to ultrafast massive photoionization. The resulting nonequilibrium state of matter has been monitored through absorption spectroscopy across the L(2,3) edge of Mg as a function of the FEL fluence. The raw spectroscopic data indicate that at about 100J/cm(2) the main absorption channels of the sample, i.e., Mg (2p→free) and oxidized Al (valence→free), are almost saturated. The spectral behavior of the induced transparency has been interpreted with an analytical approach based on an effective ionization potential of the generated solid-density plasma.

Four-wave mixing experiments with extreme ultraviolet transient gratings.

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 methods. The coherent and multi-wave nature of the FWM approach has been crucial in the development of advanced technologies, such as silicon photonics, subwavelength imaging and quantum communications. 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 resonances. 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 laser, 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 dynamics. The theoretical possibility of realizing these applications has already stimulated ongoing developments of free-electron lasers: our results show that FWM at suboptical wavelengths is feasible, and we hope that they will enable advances in present and future photon sources.