Ultrastable, high-repetition-rate attosecond beamline for time-resolved XUV-IR coincidence spectroscopy.

The implementation of attosecond photoelectron-photoion coincidence spectroscopy for the investigation of atomic and molecular dynamics calls for a high-repetition-rate driving source combined with experimental setups characterized by excellent stability for data acquisition over time intervals ranging from a few hours up to a few days. This requirement is crucial for the investigation of processes characterized by low cross sections and for the characterization of fully differential photoelectron(s) and photoion(s) angular and energy distributions. We demonstrate that the implementation of industrial-grade lasers, combined with a careful design of the delay line implemented in the pump-probe setup, allows one to reach ultrastable experimental conditions leading to an error in the estimation of the time delays of only 12 as over an acquisition time of 6.5 h. This result opens up new possibilities for the investigation of attosecond dynamics in simple quantum systems.

Attosecond photoionisation time delays reveal the anisotropy of the molecular potential in the recoil frame.

Photoionisation time delays carry structural and dynamical information on the target system, including electronic correlation effects in atoms and molecules and electron transport properties at interfaces. In molecules, the electrostatic potential experienced by an outgoing electron depends on the emission direction, which should thus lead to anisotropic time delays. To isolate this effect, information on the orientation of the molecule at the photoionisation instant is required. Here we show how attosecond time delays reflect the anisotropic molecular potential landscape in CF4 molecules. The variations in the measured delays can be directly related to the different heights of the potential barriers that the outgoing electrons see in the vicinity of shape resonances. Our results indicate the possibility to investigate the spatial characteristics of the molecular potential by mapping attosecond photoionisation time delays in the recoil-frame.

Ultrafast photoelectron spectroscopy of photoexcited aqueous ferrioxalate.

The photochemistry of metal-organic compounds in solution is determined by both intra- and inter-molecular relaxation processes after photoexcitation. Understanding its prime mechanisms is crucial to optimise the reactive paths and control their outcome. Here we investigate the photoinduced dynamics of aqueous ferrioxalate ([FeIII(C2O4)3]3-) upon 263 nm excitation using ultrafast liquid phase photoelectron spectroscopy (PES). The initial step is found to be a ligand-to-metal electron transfer, occuring on a time scale faster than our time resolution (≲30 fs). Furthermore, we observe that about 25% of the initially formed ferrous species population are lost in ∼2 ps. Cast in the contest of previous ultrafast infrared and X-ray spectroscopic studies, we suggest that upon prompt photoreduction of the metal centre, the excited molecules dissociate in <140 fs into the pair of CO2 and [(CO2)FeII(C2O4)2]3- fragments, with unity quantum yield. About 25% of these pairs geminately recombine in ∼2 ps, due to interaction with the solvent molecules, reforming the ground state of the parent ferric molecule.

Light-Induced Renormalization of the Dirac Quasiparticles in the Nodal-Line Semimetal ZrSiSe.

In nodal-line semimetals, linearly dispersing states form Dirac loops in the reciprocal space with a high degree of electron-hole symmetry and a reduced density of states near the Fermi level. The result is reduced electronic screening and enhanced correlations between Dirac quasiparticles. Here we investigate the electronic structure of ZrSiSe, by combining time- and angle-resolved photoelectron spectroscopy with ab initio density functional theory (DFT) complemented by an extended Hubbard model (DFT+U+V) and by time-dependent DFT+U+V. We show that electronic correlations are reduced on an ultrashort timescale by optical excitation of high-energy electrons-hole pairs, which transiently screen the Coulomb interaction. Our findings demonstrate an all-optical method for engineering the band structure of a quantum material.

Evidence of Large Polarons in Photoemission Band Mapping of the Perovskite Semiconductor CsPbBr_{3}.

Lead-halide perovskite (LHP) semiconductors are emergent optoelectronic materials with outstanding transport properties which are not yet fully understood. We find signatures of large polaron formation in the electronic structure of the inorganic LHP CsPbBr_{3} by means of angle-resolved photoelectron spectroscopy. The experimental valence band dispersion shows a hole effective mass of 0.26±0.02 m_{e}, 50% heavier than the bare mass m_{0}=0.17 m_{e} predicted by density functional theory. Calculations of the electron-phonon coupling indicate that phonon dressing of the carriers mainly occurs via distortions of the Pb-Br bond with a Fröhlich coupling parameter α=1.81. A good agreement with our experimental data is obtained within the Feynman polaron model, validating a viable theoretical method to predict the carrier effective mass of LHPs ab initio.

High-flux source of coherent XUV pulses for user applications.

We present experimental results obtained at a user-oriented XUV beamline implemented at the ELI Beamlines facility. The coherent XUV radiation is produced via high harmonic generation in gases in a loose focusing geometry. The beamline is designed to be driven by 1 kHz, 100 mJ, 20 fs pulses centered at a wavelength of 830 nm. Results such as XUV spectra, beam wavefront and pulse energy obtained during the beamline commissioning with a commercial 1 kHz, 5 mJ, 40 fs laser system are presented. A unique XUV spectrometer for source characterization designed to reach a very high sensitivity is described in detail, and we demonstrate a novel technique for single-shot and every-shot XUV pulse energy measurement.

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.

Tunable orbital angular momentum in high-harmonic generation.

Optical vortices are currently one of the most intensively studied topics in optics. These light beams, which carry orbital angular momentum (OAM), have been successfully utilized in the visible and infrared in a wide variety of applications. Moving to shorter wavelengths may open up completely new research directions in the areas of optical physics and material characterization. Here, we report on the generation of extreme-ultraviolet optical vortices with femtosecond duration carrying a controllable amount of OAM. From a basic physics viewpoint, our results help to resolve key questions such as the conservation of angular momentum in highly nonlinear light-matter interactions, and the disentanglement and independent control of the intrinsic and extrinsic components of the photon's angular momentum at short-wavelengths. The methods developed here will allow testing some of the recently proposed concepts such as OAM-induced dichroism, magnetic switching in organic molecules and violation of dipolar selection rules in atoms.

Laser-Assisted Photoelectric Effect from Liquids.

The laser-assisted photoelectric effect from liquid surfaces is reported for the first time. Photoelectrons generated by 35.6 eV radiation from a liquid microjet of water under vacuum are dressed with a ℏω=1.55 eV laser field. The subsequent redistribution of the photoelectron energies consists in the appearance of sidebands shifted by energies equivalent to ℏω, 2ℏω, and 3ℏω. The response has been modeled to the third order and combined with energy-resolved measurements. This result opens the possibility to investigate the dynamics at surfaces of liquid solutions and provide information about the electron emission process from a liquid.

Harmonium: A pulse preserving source of monochromatic extreme ultraviolet (30-110 eV) radiation for ultrafast photoelectron spectroscopy of liquids.

A tuneable repetition rate extreme ultraviolet source (Harmonium) for time resolved photoelectron spectroscopy of liquids is presented. High harmonic generation produces 30-110 eV photons, with fluxes ranging from ∼2 × 10(11) photons/s at 36 eV to ∼2 × 10(8) photons/s at 100 eV. Four different gratings in a time-preserving grating monochromator provide either high energy resolution (0.2 eV) or high temporal resolution (40 fs) between 30 and 110 eV. Laser assisted photoemission was used to measure the temporal response of the system. Vibrational progressions in gas phase water were measured demonstrating the ∼0.2 eV energy resolution.

Spectrometer for X-ray emission experiments at FERMI free-electron-laser.

A portable and compact photon spectrometer to be used for photon in-photon out experiments, in particular x-ray emission spectroscopy, is presented. The instrument operates in the 25-800 eV energy range to cover the full emissions of the FEL1 and FEL2 stages of FERMI. The optical design consists of two interchangeable spherical varied-lined-spaced gratings and a CCD detector. Different input sections can be accommodated, with/without an entrance slit and with/without an additional relay mirror, that allow to mount the spectrometer in different end-stations and at variable distances from the target area both at synchrotron and at free-electron-laser beamlines. The characterization on the Gas Phase beamline at ELETTRA Synchrotron (Italy) is presented.

High-throughput beamline for attosecond pulses based on toroidal mirrors with microfocusing capabilities.

We have developed a novel attosecond beamline designed for attosecond-pump/attosecond probe experiments. Microfocusing of the Extreme-ultraviolet (XUV) radiation is obtained by using a coma-compensated optical configuration based on the use of three toroidal mirrors controlled by a genetic algorithm. Trains of attosecond pulses are generated with a measured peak intensity of about 3 × 10(11) W/cm(2).

Ultrafast electron dynamics in phenylalanine initiated by attosecond pulses.

In the past decade, attosecond technology has opened up the investigation of ultrafast electronic processes in atoms, simple molecules, and solids. Here, we report the application of isolated attosecond pulses to prompt ionization of the amino acid phenylalanine and the subsequent detection of ultrafast dynamics on a sub-4.5-femtosecond temporal scale, which is shorter than the vibrational response of the molecule. The ability to initiate and observe such electronic dynamics in polyatomic molecules represents a crucial step forward in attosecond science, which is progressively moving toward the investigation of more and more complex systems.

Double-configuration grating monochromator for extreme-ultraviolet ultrafast pulses.

We present the design and characterization of a double-configuration grating monochromator for the spectral selection of extreme-ultraviolet ultrafast pulses. Two grating geometries are joined in an instrument with two interchangeable diffracting stages, both used at grazing incidence: one with the gratings in the off-plane mount (OPM), the other in the classical diffraction mount (CDM). The use of two stages gives great flexibility: the OPM stage is used for sub-50 fs time response and low spectral resolution, while the CDM stage is for 100-200 fs time response and high spectral resolution. The monochromator spectral and temporal performances have been experimentally demonstrated on a high-order laser-harmonics beam line.

CITIUS: an infrared-extreme ultraviolet light source for fundamental and applied ultrafast science.

We present the main features of CITIUS, a new light source for ultrafast science, generating tunable, intense, femtosecond pulses in the spectral range from infrared to extreme ultraviolet (XUV). The XUV pulses (about 10(5)-10(8) photons/pulse in the range 14-80 eV) are produced by laser-induced high-order harmonic generation in gas. This radiation is monochromatized by a time-preserving monochromator, also allowing one to work with high-resolution bandwidth selection. The tunable IR-UV pulses (10(12)-10(15) photons/pulse in the range 0.4-5.6 eV) are generated by an optical parametric amplifier, which is driven by a fraction of the same laser pulse that generates high order harmonics. The IR-UV and XUV pulses follow different optical paths and are eventually recombined on the sample for pump-probe experiments. We also present the results of two pump-probe experiments: with the first one, we fully characterized the temporal duration of harmonic pulses in the time-preserving configuration; with the second one, we demonstrated the possibility of using CITIUS for selective investigation of the ultra-fast dynamics of different elements in a magnetic compound.

Non-collinear high-order harmonic generation by three interfering laser beams.

High order harmonic generation (HHG) has shown its impact on several applications in Attosecond Science and Atomic and Molecular Physics. Owing to the complexity of the experimental setup for the generation and characterization of harmonics, as well as to the large computational costs of numerical modelling, HHG is generally performed and modelled in collinear geometry. Recently, several experiments have been performed exploiting non-collinear geometry, such as HHG in a grating of excited molecules created by crossing beams. In such studies, harmonics were observed at propagation directions different from those of the driving pulses; moreover the scattered harmonics were angularly dispersed.In this work we report on a new regime of HHG driven by multiple beams, where the harmonics are generated by three synchronized, intense laser pulses organized in a non-planar geometry. Although the configuration we explore is well within the strong-field regime, the scattered harmonics we observe are not angularly dispersed.

Micro-focusing of attosecond pulses by grazing-incidence toroidal mirrors.

The design of optical systems for micro-focusing of extreme-ultraviolet (XUV) attosecond pulses through grazing-incidence toroidal mirrors is presented. Aim of the proposed configuration is to provide a micro-focused image through a high demagnification of the XUV source with the following characteristics: i) almost negligible aberrations; ii) long exit arm to easily accommodate at the output the experimental setups required for the applications of the focused attosecond pulses; iii) possibility to have an intermediate region where the XUV beam is collimated, in order to insert a plane split-mirror for the generation of two XUV pulse replicas to be used in a XUV-pump/XUV-probe setup. We present the analytical and numerical study of two optical configurations characterized by two sections based on the use of toroidal mirrors. The first section provides a demagnified image of the source in an intermediate focus that is free from defocusing but has a large coma aberration. The second section consists of a relay mirror that is mounted in Z-shaped geometry with respect to the previous one, in order to give a stigmatic image with a coma that is opposite to that provided by the first section. An example is provided to demonstrate the capability to achieve spot sizes in the 5-15 µm range with a demagnification higher than 10 in a compact envelope.

High-order-harmonic generation and superradiance in a seeded free-electron laser.

Higher order harmonic generation in a free-electron laser amplifier operating in the superradiant regime [R. H. Dicke, Phys. Rev. 93, 99 (1954).] has been observed. Superradiance has been induced by seeding a single-pass amplifier with the second harmonic of a Ti:sapphire laser, generated in a ß-Barium borate crystal, at seed intensities comparable to the free-electron laser saturation intensity. Pulse energy and spectral distributions of the harmonics up to the 11th order have been measured and compared with simulations.

Active diffraction gratings: development and tests.

We present the realization and characterization of an active spherical diffraction grating with variable radius of curvature to be used in grazing-incidence monochromators. The device consists of a bimorph deformable mirror on the top of which a diffraction grating with laminar profile is realized by UV lithography. The experimental results show that the active grating can optimize the beam focalization of visible wavelengths through its rotation and focus accommodation.

High-gain harmonic-generation free-electron laser seeded by harmonics generated in gas.

The injection of a seed in a free-electron laser (FEL) amplifier reduces the saturation length and improves the longitudinal coherence. A cascaded FEL, operating in the high-gain harmonic-generation regime, allows us to extend the beneficial effects of the seed to shorter wavelengths. We report on the first operation of a high-gain harmonic-generation free-electron laser, seeded with harmonics generated in gas. The third harmonics of a Ti:sapphire laser, generated in a gas cell, has been amplified and up-converted to its second harmonic (λ(rad)=133 nm) in a FEL cascaded configuration based on a variable number of modulators and radiators. We studied the transition between coherent harmonic generation and superradiant regime, optimizing the laser performances with respect to the number of modulators and radiators.