A setup for hard x-ray time-resolved resonant inelastic x-ray scattering at SwissFEL.

We present a new setup for resonant inelastic hard x-ray scattering at the Bernina beamline of SwissFEL with energy, momentum, and temporal resolution. The compact R = 0.5 m Johann-type spectrometer can be equipped with up to three crystal analyzers and allows efficient collection of RIXS spectra. Optical pumping for time-resolved studies can be realized with a broad span of optical wavelengths. We demonstrate the performance of the setup at an overall ∼180 meV resolution in a study of ground-state and photoexcited (at 400 nm) honeycomb 5d iridate α-Li2IrO3. Steady-state RIXS spectra at the iridium L3-edge (11.214 keV) have been collected and are in very good agreement with data collected at synchrotrons. The time-resolved RIXS transients exhibit changes in the energy loss region <2 eV, whose features mostly result from the hopping nature of 5d electrons in the honeycomb lattice. These changes are ascribed to modulations of the Ir-to-Ir inter-site transition scattering efficiency, which we associate to a transient screening of the on-site Coulomb interaction.

Non-equilibrium dynamics of spin-lattice coupling.

Quantifying the dynamics of normal modes and how they interact with other excitations is of central importance in condensed matter. Spin-lattice coupling is relevant to several sub-fields of condensed matter physics; examples include spintronics, high-Tc superconductivity, and topological materials. However, experimental approaches that can directly measure it are rare and incomplete. Here we use time-resolved X-ray diffraction to directly access the ultrafast motion of atoms and spins following the coherent excitation of an electromagnon in a multiferroic hexaferrite. One striking outcome is the different phase shifts relative to the driving field of the two different components. This phase shift provides insight into the excitation process of such a coupled mode. This direct observation of combined lattice and magnetization dynamics paves the way to access the mode-selective spin-lattice coupling strength, which remains a missing fundamental parameter for ultrafast control of magnetism and is relevant to a wide variety of materials.

Anomalous temperature dependence of the experimental x-ray structure factor of supercooled water.

The structural changes of water upon deep supercooling were studied through wide-angle x-ray scattering at SwissFEL. The experimental setup had a momentum transfer range of 4.5 Å-1, which covered the principal doublet of the x-ray structure factor of water. The oxygen-oxygen structure factor was obtained for temperatures down to 228.5 ± 0.6 K. Similar to previous studies, the second diffraction peak increased strongly in amplitude as the structural change accelerated toward a local tetrahedral structure upon deep supercooling. We also observed an anomalous trend for the second peak position of the oxygen-oxygen structure factor (q2). We found that q2 exhibits an unprecedented positive partial derivative with respect to temperature for temperatures below 236 K. Based on Fourier inversion of our experimental data combined with reference data, we propose that the anomalous q2 shift originates from that a repeat spacing in the tetrahedral network, associated with all peaks in the oxygen-oxygen pair-correlation function, gives rise to a less dense local ordering that resembles that of low-density amorphous ice. The findings are consistent with that liquid water consists of a pentamer-based hydrogen-bonded network with low density upon deep supercooling.

Deriving x-ray pulse duration from center-of-energy shifts in THz-streaked ionized electron spectra.

A fast and robust, yet simple, method has been developed for the immediate characterization of x-ray pulse durations via IR/THz streaking that uses the center of energy (COE) of the photoelectron spectrum for the evaluation. The manuscript presents theory and numerical models demonstrating that the maximum COEs shift as a function of the pulse duration and compares them to existing data for validation. It further establishes that the maximum COE can be derived from two COE measurements set at a phase of π/2 apart. The theory, model, and data agree with each other very well, and they present a way to measure pulse durations ranging from sub-fs to tens of fs on-the-fly with a fairly simple experimental setup.

New insights into correlated materials in the time domain-combining far-infrared excitation with x-ray probes at cryogenic temperatures.

Modern techniques for the investigation of correlated materials in the time domain combine selective excitation in the THz frequency range with selective probing of coupled structural, electronic and magnetic degrees of freedom using x-ray scattering techniques. Cryogenic sample temperatures are commonly required to prevent thermal occupation of the low energy modes and to access relevant material ground states. Here, we present a chamber optimized for high-field THz excitation and (resonant) x-ray diffraction at sample temperatures between 5 and 500 K. Directly connected to the beamline vacuum and featuring both a Beryllium window and an in-vacuum detector, the chamber covers the full (2-12.7) keV energy range of the femtosecond x-ray pulses available at the Bernina endstation of the SwissFEL free electron laser. Successful commissioning experiments made use of the energy tunability to selectively track the dynamics of the structural, magnetic and orbital order of Ca2RuO4and Tb2Ti2O7at the Ru (2.96 keV) and Tb (7.55 keV)L-edges, respectively. THz field amplitudes up to 1.12 MV cm-1peak field were demonstrated and used to excite the samples at temperatures as low as 5 K.

Enhancement and maximum in the isobaric specific-heat capacity measurements of deeply supercooled water using ultrafast calorimetry.

Knowledge of the temperature dependence of the isobaric specific heat (Cp) upon deep supercooling can give insights regarding the anomalous properties of water. If a maximum in Cp exists at a specific temperature, as in the isothermal compressibility, it would further validate the liquid-liquid critical point model that can explain the anomalous increase in thermodynamic response functions. The challenge is that the relevant temperature range falls in the region where ice crystallization becomes rapid, which has previously excluded experiments. Here, we have utilized a methodology of ultrafast calorimetry by determining the temperature jump from femtosecond X-ray pulses after heating with an infrared laser pulse and with a sufficiently long time delay between the pulses to allow measurements at constant pressure. Evaporative cooling of ∼15-µm diameter droplets in vacuum enabled us to reach a temperature down to ∼228 K with a small fraction of the droplets remaining unfrozen. We observed a sharp increase in Cp, from 88 J/mol/K at 244 K to about 218 J/mol/K at 229 K where a maximum is seen. The Cp maximum is at a similar temperature as the maxima of the isothermal compressibility and correlation length. From the Cp measurement, we estimated the excess entropy and self-diffusion coefficient of water and these properties decrease rapidly below 235 K.

Laser-induced inner-shell excitations through direct electron re-collision versus indirect collision.

The dynamics and the decay processes of inner-shell excited atoms are of great interest in physics, chemistry, biology, and technology. The highly excited state decays very quickly through different channels, both radiative and non-radiative. It is therefore a long-standing goal to study such dynamics directly in the time domain. Using few-cycle infrared laser pulses, we investigated the excitation and ionization of inner-shell electrons through laser-induced electron re-collision with the original parent ions and measured the dependence of the emitted x-ray spectra on the intensity and ellipticity of the driving laser. These directly re-colliding electrons can be used as the initiating pump step in pump/probe experiments for studying core-hole dynamics at their natural temporal scale. In our experiment we found that the dependence of the x-ray emission spectrum on the laser intensity and polarization state varies distinctly for the two kinds of atomic systems. Relying on our data and numerical simulations, we explain this behavior by the presence of different excitation mechanisms that are contributing in different ratios to the respective overall x-ray emission yields. Direct re-collision excitation competes with indirect collisions with neighboring atoms by electrons having "drifted away" from the original parent ion.

Optical second harmonic generation in LiB3O5 modulated by intense femtosecond X-ray pulses.

Many of the scientific applications for X-ray free-electron lasers seek to exploit the ultrashort pulse durations of intense X-rays to obtain femtosecond time resolution of various processes in a "pump-probe" scheme. One of the limiting factors for such experiments is the timing jitter between the X-rays and ultrashort pulses from more conventional lasers operating at near-optical wavelengths. In this work, we investigate the potential of using X-ray-induced changes in the optical second harmonic generation efficiency of a nonlinear crystal to retrieve single-shot arrival times of X-ray pulses with respect to optical laser pulses. Our experimental results and simulations show changes to the efficiency of the second harmonic generation of 12%, approximately three times larger than the measured changes in the transmission of the 800 nm center-wavelength fundamental pulse. Further experiments showing even larger changes in the transmission of 400 nm center-wavelength pulses show that the mechanism of the second harmonic generation efficiency modulation is mainly the result of X-ray-induced changes in the linear absorption coefficients near 400 nm. We demonstrate and characterize a cross-correlation tool based on this effect in reference to a previously demonstrated method of X-ray/optical cross-correlation.

Experimental station Bernina at SwissFEL: condensed matter physics on femtosecond time scales investigated by X-ray diffraction and spectroscopic methods.

The Bernina instrument at the SwissFEL Aramis hard X-ray free-electron laser is designed for studying ultrafast phenomena in condensed matter and material science. Ultrashort pulses from an optical laser system covering a large wavelength range can be used to generate specific non-equilibrium states, whose subsequent temporal evolution can be probed by selective X-ray scattering techniques in the range 2-12 keV. For that purpose, the X-ray beamline is equipped with optical elements which tailor the X-ray beam size and energy, as well as with pulse-to-pulse diagnostics that monitor the X-ray pulse intensity, position, as well as its spectral and temporal properties. The experiments can be performed using multiple interchangeable endstations differing in specialization, diffractometer and X-ray analyser configuration and load capacity for specialized sample environment. After testing the instrument in a series of pilot experiments in 2018, regular user operation begins in 2019.

Dynamics of the photoinduced insulator-to-metal transition in a nickelate film.

Material properties can be controlled via strain, pressure, chemical composition, or dimensionality. Nickelates are particularly susceptible due to their strong variations of the electronic and magnetic properties on such external stimuli. Here, we analyze the photoinduced dynamics in a single crystalline NdNiO3 film upon excitation across the electronic gap. Using time-resolved reflectivity and resonant x-ray diffraction, we show that the pump pulse induces an insulator-to-metal transition, accompanied by the melting of the charge order. Finally, we compare our results with similar studies in manganites and show that the same model can be used to describe the dynamics in nickelates, hinting towards a unified description of these photoinduced electronic ordering phase transitions.

Opportunities for Chemistry at the SwissFEL X-ray Free Electron Laser.

X-ray techniques have long been applied to chemical research, ranging from powder diffraction tools to analyse material structure to X-ray fluorescence measurements for sample composition. The development of high-brightness, accelerator-based X-ray sources has allowed chemists to use similar techniques but on more demanding samples and using more photon-hungry methods. X-ray Free Electron Lasers (XFELs) are the latest in the development of these large-scale user facilities, opening up new avenues of research and the possibility of more advanced applications for a range of research. The SwissFEL XFEL project at the Paul Scherrer Institute will begin user operation in the hard X-ray (2.1-12.4 keV) photon energy range in 2018 with soft X-ray (240-1930 eV) user operation to follow and here we will present the details of this project, it's operating capabilities, and some aspects of the experimental stations that will be particularly attractive for chemistry research. SwissFEL is a revolutionary new machine that will complement and extend the time-resolved chemistry efforts in the Swiss research community.

Ultrafast Excitation of an Inner-Shell Electron by Laser-Induced Electron Recollision.

Extreme ultraviolet attosecond pulses, generated by a process known as laser-induced electron recollision, are a key ingredient for attosecond metrology, providing a tool to precisely initiate and probe subfemtosecond dynamics in atoms, molecules, and solids. However, extending attosecond metrology to scrutinize the dynamics of the inner-shell electrons is a challenge, that is because of the lower efficiency in generating the required soft x-ray (ℏω>300 eV) attosecond bursts. A way around this problem is to use the recolliding electron to directly initiate the desired inner-shell process, instead of using the currently low flux x-ray attosecond sources. Such an excitation process occurs in a subfemtosecond time scale, and may provide the necessary "pump" step in a pump-probe experiment. Here we used a few cycle infrared (λ_{0}≈1800 nm) source and observed direct evidence for inner-shell excitations through the laser-induced electron recollision process. It is the first step toward time-resolved core-hole studies in the keV energy range with subfemtosecond time resolution.

500 kHz OPCPA delivering tunable sub-20 fs pulses with 15 W average power based on an all-ytterbium laser.

An optical parametric chirped pulse amplifier fully based on Yb lasers at 500 kHz is described. Passive optical-synchronization is achieved between a fiber laser-pumped white-light and a 515 nm pump produced with a 200 W picosecond Yb:YAG InnoSlab amplifier. An output power up to 19.7 W with long-term stability of 0.3% is demonstrated for wavelength tunable pulses between 680 nm and 900 nm and spectral stability of 0.2%; 16.5 W can be achieved with a bandwidth supporting 5.4 fs pulses. We demonstrate compression of 30 µJ pulses to sub-20 fs duration with a prism compressor, suitable for high harmonic generation.

Observation of CEP effect via filamentation in transparent solids.

We report on the first direct observation of carrier-envelope-phase (CEP) effect during the interaction between few-cycle laser pulses and bulk solid materials. Using 2-cycle mid-infrared laser pulses with stabilized CEP, the CEP effect of tunneling ionization during the laser filamentation in a fused silica is revealed. The phase variation of the accompanying supercontinuum (SC) emission with filamentation at different CEPs of laser pulses can be measured by means of spectral interference technique, as a direct manifestation of the strong field tunneling ionization dynamics in transparent solids.

Carrier-envelope-phase-stable, 1.2 mJ, 1.5 cycle laser pulses at 2.1 µm.

We produce 1.5 cycle (10.5 fs), 1.2 mJ, 3 kHz carrier-envelope-phase-stable pulses at 2.1 µm carrier wavelength, from a three-stage optical parametric chirped-pulse amplifier system, pumped by an optically synchronized 1.6 ps Yb:YAG thin disk laser. A chirped periodically poled lithium niobate crystal is used to generate the ultrabroad spectrum needed for a 1.5 cycle pulse through difference frequency mixing of spectrally broadened pulse from a Ti:sapphire amplifier. It will be an ideal tool for producing isolated attosecond pulses with high photon energies.

Active stabilization for optically synchronized optical parametric chirped pulse amplification.

The development of new high power laser sources tends toward optical parametric chirped pulse amplification (OPCPA) in recent years. One of the difficulties in OPCPA is the the temporal overlap between pump and seed pulses. In this work we characterize our timing jitter on a single-shot basis using spectrally resolved cross-correlation in combination with a position sensitive detector. A commercial beam stabilization is adapted to actively enhance temporal overlap. This delay-stabilizer reduces the RMS jitter from σ = 127 fs down to σ = 24 fs. The enhanced temporal overlap is demonstrated in our frontend and we propose the scheme to be applicable in many optically synchronized high-repetition-rate OPCPA systems.

Subfemtosecond K-shell excitation with a few-cycle infrared laser field.

Subfemtosecond bursts of extreme ultraviolet radiation, facilitated by a process known as high-order harmonic generation, are a key ingredient for attosecond metrology, providing a tool to precisely initiate and probe ultrafast dynamics in the microcosms of atoms, molecules, and solids. These ultrashort pulses are always, and as a by-product of the way they are generated, accompanied by laser-induced recollisions of electrons with their parent ions. By using a few-cycle infrared (λ(0)=2.1 µm) driving laser, we were able to directly excite high-energy (∼870 eV) inner-shell electrons through laser-induced electron recollision, opening the door to time-resolved studies of core-level and concomitant multielectron dynamics.

Generation of carrier-envelope-phase-stable 2-cycle 740-microJ pulses at 2.1-microm carrier wavelength.

We produce carrier-envelope-phase-stable 15.7-fs (2-cycle) 740-microJ pulses at the 2.1-microm carrier wavelength, from a three-stage optical parametric chirped-pulse amplifier system, pumped by an optically synchronized 49-ps 11-mJ Nd:YLF laser. A novel seed pulse spectral shaping method is used to ascertain the true amplified seed energy and the parametric superfluorescence levels.

Long lifetime plasma channel in air generated by multiple femtosecond laser pulses and an external electrical field.

The lifetime of a plasma channel produced by self-guiding intense femtosecond laser pulses in air is largely prolonged by adding a high voltage electrical field in the plasma and by introducing a series of femtosecond laser pulses. An optimal lifetime value is realized through adjusting the delay among these laser pulses. The lifetime of a plasma channel is greatly enhanced to 350 ns by using four sequential intense 100fs(FWHM) laser pulses with an external electrical field of about 350kV/m, which proves the feasibility of prolonging the lifetime of plasma by adding an external electrical field and employing multiple laser pulses.

Time-resolved investigation of low-density plasma channels produced by a kilohertz femtosecond laser in air.

By employing pump-probe back longitudinal diffractometry, the electron density and decay dynamics of a weak plasma channel created by a 1-KHz fs laser in air has been investigated. With ultrashort laser pulses of 50 fs and low energy of 0.6 mJ, we observe weak plasma channels with a length approximately 2 cm in air. An analytical reconstruction method of electron density has been analyzed, which is sensitive to the phase shift and channel size. The electron density in the weak plasma channel is extracted to be about 4 x 10(16) cm(-3). The diameters of the plasma channel and the filament are about 50 and 150 microm, respectively, and the measurable electron density can be extended to less than 10(15) cm(-3). Moreover, a different time-frequency technique called linearly chirped longitudinal diffractometry is proposed to time-resolved investigate ultrafast ionization dynamics of laser-irradiated gas, laser interaction with cluster beam, etc.