Determination of the electronic structure of mass-selected transient molecular ions which can be considered as building blocks of biomolecules.

With the intense and coherent x-ray pulses available from free-electron lasers, the possibility to transfer non-linear spectroscopic methods from the laser lab to the x-ray world arises. Advantages especially regarding selectivity and thus information content as well as an improvement of signal levels are expected. The use of coherences is especially fruitful and the example of coherent x-ray/optical sum-frequency generation is discussed. However, many non-linear x-ray methods still await discovery, partially due to the necessity for extremely adaptable and versatile instrumentation that can be brought to free-electron lasers for the analysis of the spectral content emitted from the sample into a continuous range of emission angles. Such an instrument (called MUSIX) is being developed and employed at FLASH, the free-electron laser in Hamburg and is described in this contribution together with first results.

The F 1s core level photoionization of the ionic molecular radical HF + has been studied using the photon−ion merged-beams technique at a synchrotron radiation source. Upon analyzing kinetic energy release (KER) dependent photoion yield spectra, complex ultrafast dissociation dynamics of the F 1s core hole excited σ* state can be revealed. By means of configuration−interaction electronic structure calculations of the excited molecular potential energy curves, this complex process can be attributed to a spin-dependent dissociation of the excited σ* biradical state.

X-ray absorption spectroscopy (XAS) and the directly linked X-ray reflectivity near absorption edges yield a wealth of specific information on the electronic structure around the resonantly addressed element. Observing the dynamic response of complex materials to optical excitations in pump–probe experiments requires high sensitivity to small changes in the spectra which in turn necessitates the brilliance of free electron laser (FEL) pulses. However, due to the fluctuating spectral content of pulses generated by self-amplified spontaneous emission (SASE), FEL experiments often struggle to reach the full sensitivity and time-resolution that FELs can in principle enable. Here, we implement a setup which solves two common challenges in this type of spectroscopy using FELs: First, we achieve a high spectral resolution by using a spectrometer downstream of the sample instead of a monochromator upstream of the sample. Thus, the full FEL bandwidth contributes to the measurement at the same time, and the FEL pulse duration is not elongated by a monochromator. Second, the FEL beam is divided into identical copies by a transmission grating beam splitter so that two spectra from separate spots on the sample (or from the sample and known reference) can be recorded in-parallel with the same spectrometer, enabling a spectrally resolved intensity normalization of pulse fluctuations in pump–probe scenarios. We analyze the capabilities of this setup around the oxygen K- and nickel L-edges recorded with third harmonic radiation of the free electron laser in Hamburg (FLASH), demonstrating the capability for pump–probe measurements with sensitivity to reflectivity changes on the per mill level.

We present the experimental end-station TRIXS dedicated to time-resolved soft x-ray resonant inelastic x-ray scattering (RIXS) experiments on solid samples at the free-electron laser FLASH. Using monochromatized ultrashort femtosecond XUV/soft x-ray photon pulses in combination with a synchronized optical laser in a pump-probe scheme, the TRIXS setup allows measuring sub-picosecond time-resolved high-resolution RIXS spectra in the energy range from 35 eV to 210 eV, thus spanning the M-edge (M 1 and M 2,3 ) absorption resonances of 3d transition metals and N 4,5 -edges of rare earth elements. A Kirkpatrick–Baez refocusing mirror system at the first branch of the plane grating monochromator beamline (PG1) provides a focus of (6 × 6) μ m 2 (FWHM) at the sample. The RIXS spectrometer reaches an energy resolution of 35–160 meV over the entire spectral range. The optical laser system based on a chirped pulse optical parametric amplifier provides approximately 100 fs (FWHM) long photon pulses at the fundamental wavelength of 800 nm and a fluence of 120 mJ/cm 2 at a sample for optical pump-XUV probe measurements. Furthermore, optical frequency conversion enables experiments at 400 nm or 267 nm with a fluence of 80 and 30 mJ/cm 2 , respectively. Some of the first (pump-probe) RIXS spectra measured with this setup are shown. The measured time resolution for time-resolved RIXS measurements has been characterized as 287 fs (FWHM) for the used energy resolution.

Soft x-ray spectroscopy is invaluable for gaining insight into quantum materials. However, it is typically conducted in a spatially averaging way, making it blind to inhomogeneity in samples. Here, we demonstrate how we couple imaging to x-ray absorption spectroscopy and resonant inelastic x-ray scattering. Accordingly, we use a 2D detector and an off-axis Fresnel zone plate that images the sample in one spatial dimension and provides spectroscopic information in the other dimension. With our setup, we envision to enable a more detailed understanding of how the behavior of microscopic domains determines the functionality of quantum materials.

Yields of atomic iodine I q+ (q Z 2) fragments resulting from photoexcitation and photoionisation of the target cations CH x I + (x = 0-3) have been measured in the photon-energy range 610 eV to 670 eV, which comprises the threshold for iodine 3d ionisation. The measured ion-yield spectra show two strong and broad resonance features due to the excitation of the 3d 3/2,5/2 electrons into ef states similar to atomic iodine. In the 3d pre-edge range, electrons are excited into molecular orbitals consisting of iodine, carbon, and hydrogen atomic orbitals. These transitions have been identified by comparison with literature data and by simulations using time-dependent density functional theory (TDDFT) with the KMLYP functional. The ion-yield spectrum for CH 3 I + resembles the spectrum of IH + [Klumpp et al., Phys.Rev. A, 2018, 97, 033401] because the highest occupied molecular orbitals (HOMO) of the H and CH 3 fragments both contain a single vacancy, only. For the molecular cations with higher number of vacancies in the valence molecular orbitals CH x I + (x = 0-2), a stronger hybridisation of the molecular orbitals occurs between the organic fragment and the iodine resulting in a change of bonding from a single s bond in CH 3 I + to a triple bond including two p orbitals in CI + . This is reflected in the resonance energies of the observed absorption lines below the iodine 3d excitation threshold.

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.