Optical control of 4f orbital state in rare-earth metals.

A change of orbital state alters the coupling between ions and their surroundings drastically. Orbital excitations are hence key to understand and control interaction of ions. Rare-earth elements with strong magneto-crystalline anisotropy (MCA) are important ingredients for magnetic devices. Thus, control of their localized 4f magnetic moments and anisotropy is one major challenge in ultrafast spin physics. With time-resolved x-ray absorption and resonant inelastic scattering experiments, we show for Tb metal that 4f-electronic excitations out of the ground-state multiplet occur after optical pumping. These excitations are driven by inelastic 5d-4f-electron scattering, altering the 4f-orbital state and consequently the MCA with important implications for magnetization dynamics in 4f-metals and more general for the excitation of localized electronic states in correlated materials.

Real-time observation of non-equilibrium phonon-electron energy and angular momentum flow in laser-heated nickel.

Identifying the microscopic nature of non-equilibrium energy transfer mechanisms among electronic, spin, and lattice degrees of freedom is central to understanding ultrafast phenomena such as manipulating magnetism on the femtosecond timescale. Here, we use time- and angle-resolved photoemission spectroscopy to go beyond the often-used ensemble-averaged view of non-equilibrium dynamics in terms of quasiparticle temperature evolutions. We show for ferromagnetic Ni that the non-equilibrium electron and spin dynamics display pronounced variations with electron momentum, whereas the magnetic exchange interaction remains isotropic. This highlights the influence of lattice-mediated scattering processes and opens a pathway toward unraveling the still elusive microscopic mechanism of spin-lattice angular momentum transfer.

Photoinduced Dynamics at the Water/TiO_{2}(101) Interface.

We present a femtosecond time-resolved optical pump-soft x-ray probe photoemission study in which we follow the dynamics of charge transfer at the interface of water and anatase TiO_{2}(101). By combining our observation of transient oxygen O 1s core level peak shifts at submonolayer water coverages with Ehrenfest molecular dynamics simulations we find that ultrafast interfacial hole transfer from TiO_{2} to molecularly adsorbed water is completed within the 285 fs time resolution of the experiment. This is facilitated by the formation of a new hydrogen bond between an O_{2c} site at the surface and a physisorbed water molecule. The calculations fully corroborate our experimental observations and further suggest that this process is preceded by the efficient trapping of the hole at the surface of TiO_{2} by hydroxyl species (-OH), that form following the dissociative adsorption of water. At a water coverage exceeding a monolayer, interfacial charge transfer is suppressed. Our findings are directly applicable to a wide range of photocatalytic systems in which water plays a critical role.

Ultrafast manipulation of the NiO antiferromagnetic order via sub-gap optical excitation.

Wide-band-gap insulators such as NiO offer the exciting prospect of coherently manipulating electronic correlations with strong optical fields. Contrary to metals where rapid dephasing of optical excitation via electronic processes occurs, the sub-gap excitation in charge-transfer insulators has been shown to couple to low-energy bosonic excitations. However, it is currently unknown if the bosonic dressing field is composed of phonons or magnons. Here we use the prototypical charge-transfer insulator NiO to demonstrate that 1.5 eV sub-gap optical excitation leads to a renormalised NiO band-gap in combination with a significant reduction of the antiferromagnetic order. We employ element-specific X-ray reflectivity at the FLASH free-electron laser to demonstrate the reduction of the upper band-edge at the O 1s-2p core-valence resonance (K-edge) whereas the antiferromagnetic order is probed via X-ray magnetic linear dichroism (XMLD) at the Ni 2p-3d resonance (L2-edge). Comparing the transient XMLD spectral line shape to ground-state measurements allows us to extract a spin temperature rise of 65 ± 5 K for time delays longer than 400 fs while at earlier times a non-equilibrium spin state is formed. We identify transient mid-gap states being formed during the first 200 fs accompanied by a band-gap reduction lasting at least up to the maximum measured time delay of 2.4 ps. Electronic structure calculations indicate that magnon excitations significantly contribute to the reduction of the NiO band gap.

Probing electron and hole colocalization by resonant four-wave mixing spectroscopy in the extreme ultraviolet.

Extending nonlinear spectroscopic techniques into the x-ray domain promises unique insight into photoexcited charge dynamics, which are of fundamental and applied interest. We report on the observation of a third-order nonlinear process in lithium fluoride (LiF) at a free-electron laser. Exploring the yield of four-wave mixing (FWM) in resonance with transitions to strongly localized core exciton states versus delocalized Bloch states, we find resonant FWM to be a sensitive probe for the degree of charge localization: Substantial sum- and difference-frequency generation is observed exclusively when in a one- or three-photon resonance with a LiF core exciton, with a dipole forbidden transition affecting details of the nonlinear response. Our reflective geometry-based approach to detect FWM signals enables the study of a wide variety of condensed matter sample systems, provides atomic selectivity via resonant transitions, and can be easily scaled to shorter wavelengths at free-electron x-ray lasers.

Shot noise limited soft x-ray absorption spectroscopy in solution at a SASE-FEL using a transmission grating beam splitter.

X-ray absorption near-edge structure (XANES) spectroscopy provides element specificity and is a powerful experimental method to probe local unoccupied electronic structures. In the soft x-ray regime, it is especially well suited for the study of 3d-metals and light elements such as nitrogen. Recent developments in vacuum-compatible liquid flat jets have facilitated soft x-ray transmission spectroscopy on molecules in solution, providing information on valence charge distributions of heteroatoms and metal centers. Here, we demonstrate XANES spectroscopy of molecules in solution at the nitrogen K-edge, performed at FLASH, the Free-Electron Laser (FEL) in Hamburg. A split-beam referencing scheme optimally characterizes the strong shot-to-shot fluctuations intrinsic to the process of self-amplified spontaneous emission on which most FELs are based. Due to this normalization, a sensitivity of 1% relative transmission change is achieved, limited by fundamental photon shot noise. The effective FEL bandwidth is increased by streaking the electron energy over the FEL pulse train to measure a wider spectral window without changing FEL parameters. We propose modifications to the experimental setup with the potential of improving the instrument sensitivity by two orders of magnitude, thereby exploiting the high peak fluence of FELs to enable unprecedented sensitivity for femtosecond XANES spectroscopy on liquids in the soft x-ray spectral region.

Normalized single-shot X-ray absorption spectroscopy at a free-electron laser.

A setup for dispersive X-ray absorption spectroscopy (XAS), employing a new reference scheme, has been implemented and tested at the soft X-ray free-electron laser (FEL) FLASH in Hamburg. A transmission grating was used to split the FEL beam into two copies (signal and reference). The spectral content of both beams was simultaneously measured for intensity normalization within the FEL bandwidth on a shot-to-shot basis. Excellent correlation between the two beams was demonstrated within a few percent for single bunch operation at 143 eV photon energy. Applying the normalization scheme, an absorption spectrum of a Gd2O3thin film sample was recorded around the Gd N4,5-edge photon energy of 143 eV, showing excellent agreement with a reference spectrum measured at a synchrotron. This scheme opens the door for time-resolved single-shot XAS with femtosecond time resolution at FELs.

Alignment of the aberration-free XUV Raman spectrometer at FLASH.

An extreme-ultraviolet (XUV) double-stage Raman spectrometer is permanently installed as an experimental end-station at the PG1 beamline of the soft X-ray/XUV free-electron laser in Hamburg, FLASH. The monochromator stages are designed according to the Czerny-Turner optical scheme, adapted for the XUV photon energy range, with optical elements installed at grazing-incidence angles. Such an optical scheme along with the usage of off-axis parabolic mirrors for light collimation and focusing allows for aberration-free spectral imaging on the optical axis. Combining the two monochromators in additive dispersion mode allows for reaching high resolution and superior stray light rejection, but puts high demands on the quality of the optical alignment. In order to align the instrument with the highest precision and to quantitatively characterize the instrument performance and thus the quality of the alignment, optical laser interferometry, Hartmann-Shack wavefront-sensing measurements as well as off-line soft X-ray measurements and extensive optical simulations were conducted. In this paper the concept of the alignment scheme and the procedure of the internal optical alignment are presented. Furthermore, results on the imaging quality and resolution of the first monochromator stage are shown.

CAMP@FLASH: an end-station for imaging, electron- and ion-spectroscopy, and pump-probe experiments at the FLASH free-electron laser.

The non-monochromatic beamline BL1 at the FLASH free-electron laser facility at DESY was upgraded with new transport and focusing optics, and a new permanent end-station, CAMP, was installed. This multi-purpose instrument is optimized for electron- and ion-spectroscopy, imaging and pump-probe experiments at free-electron lasers. It can be equipped with various electron- and ion-spectrometers, along with large-area single-photon-counting pnCCD X-ray detectors, thus enabling a wide range of experiments from atomic, molecular, and cluster physics to material and energy science, chemistry and biology. Here, an overview of the layout, the beam transport and focusing capabilities, and the experimental possibilities of this new end-station are presented, as well as results from its commissioning.

Diffraction gratings metrology and ray-tracing results for an XUV Raman spectrometer at FLASH.

The extreme-ultraviolet double-stage imaging Raman spectrometer is a permanent experimental endstation at the plane-grating monochromator beamline branch PG1 at FLASH at DESY in Hamburg, Germany. This unique instrument covers the photon energy range from 20 to 200 eV with high energy resolution of about 2 to 20 meV (design values) featuring an efficient elastic line suppression as well as effective stray light rejection. Such a design enables studies of low-energy excitations like, for example, phonons in solids close to the vicinity of the elastic line. The Raman spectrometer effectively operates with four reflective off-axial parabolic mirrors and two plane-grating units. The optics quality and their precise alignment are crucial to guarantee best performance of the instrument. Here, results on a comprehensive investigation of the quality of the spectrometer diffraction gratings are presented. The gratings have been characterized by ex situ metrology at the BESSY-II Optics Laboratory, employing slope measuring deflectometry and interferometry as well as atomic force microscopy studies. The efficiency of these key optical elements has been measured at the at-wavelength metrology laboratory using the reflectometer at the BESSY-II Optics beamline. Also, the metrology results are discussed with respect to the expected resolving power of the instrument by including them in ray-tracing studies of the instrument.

A non-invasive online photoionization spectrometer for FLASH2.

The stochastic nature of the self-amplified spontaneous emission (SASE) process of free-electron lasers (FELs) effects pulse-to-pulse fluctuations of the radiation properties, such as the photon energy, which are determinative for processes of photon-matter interactions. Hence, SASE FEL sources pose a great challenge for scientific investigations, since experimenters need to obtain precise real-time feedback of these properties for each individual photon bunch for interpretation of the experimental data. Furthermore, any device developed to deliver the according information should not significantly interfere with or degrade the FEL beam. Regarding the spectral properties, a device for online monitoring of FEL wavelengths has been developed for FLASH2, which is based on photoionization of gaseous targets and the measurements of the corresponding electron and ion time-of-flight spectra. This paper presents experimental studies and cross-calibration measurements demonstrating the viability of this online photoionization spectrometer.

Microfocusing at the PG1 beamline at FLASH.

The Kirkpatrick-Baez (KB) refocusing mirror system installed at the PG1 branch of the plane-grating monochromator beamline at the soft X-ray/XUV free-electron laser in Hamburg (FLASH) is designed to provide tight aberration-free focusing down to 4 µm × 6 µm full width at half-maximum (FWHM) on the sample. Such a focal spot size is mandatory to achieve ultimate resolution and to guarantee best performance of the vacuum-ultraviolet (VUV) off-axis parabolic double-monochromator Raman spectrometer permanently installed at the PG1 beamline as an experimental end-station. The vertical beam size on the sample of the Raman spectrometer, which operates without entrance slit, defines and limits the energy resolution of the instrument which has an unprecedented design value of 2 meV for photon energies below 70 eV and about 15 meV for higher energies up to 200 eV. In order to reach the designed focal spot size of 4 µm FWHM (vertically) and to hold the highest spectrometer resolution, special fully motorized in-vacuum manipulators for the KB mirror holders have been developed and the optics have been aligned employing wavefront-sensing techniques as well as ablative imprints analysis. Aberrations like astigmatism were minimized. In this article the design and layout of the KB mirror manipulators, the alignment procedure as well as microfocus optimization results are presented.

Extreme-ultraviolet compact spectrometer for the characterization of the harmonics content in the free-electron-laser radiation at FLASH.

The design and the commissioning results of a portable and compact spectrometer for the high harmonics content characterization of the extreme-ultraviolet radiation of FLASH (free-electron laser in DESY, Hamburg, Germany) are presented. The instrument is a grazing-incidence flat-field spectrometer equipped with two variable-line-spaced gratings; it covers the 2-40 nm wavelength region with a spectral resolution in the 0.1-0.2% range. Both spectral and intensity fluctuations of the fundamental emission and the harmonics are monitored.