Martin Beye

Temporal cross-correlation of x-ray free electron and optical lasers using soft x-ray pulse induced transient reflectivity.

The recent development of x-ray free electron lasers providing coherent, femtosecond-long pulses of high brilliance and variable energy opens new areas of scientific research in a variety of disciplines such as physics, chemistry, and biology. Pump-probe experimental techniques which observe the temporal evolution of systems after optical or x-ray pulse excitation are one of the main experimental schemes currently in use for ultrafast studies. The key challenge in these experiments is to reliably achieve temporal and spatial overlap of the x-ray and optical pulses. Here we present measurements of the x-ray pulse induced transient change of optical reflectivity from a variety of materials covering the soft x-ray photon energy range from 500eV to 2000eV and outline the use of this technique to establish and characterize temporal synchronization of the optical-laser and FEL x-ray pulses.

X-ray emission spectroscopy of bulk liquid water in “no-man’s land”

The structure of bulk liquid water was recently probed by x-ray scattering below the temperature limit of homogeneous nucleation (TH) of ∼232 K [J. A. Sellberg et al., Nature 510, 381-384 (2014)]. Here, we utilize a similar approach to study the structure of bulk liquid water below TH using oxygen K-edge x-ray emission spectroscopy (XES). Based on previous XES experiments [T. Tokushima et al., Chem. Phys. Lett. 460, 387-400 (2008)] at higher temperatures, we expected the ratio of the 1b1 and 1b1″ peaks associated with the lone-pair orbital in water to change strongly upon deep supercooling as the coordination of the hydrogen (H-) bonds becomes tetrahedral. In contrast, we observed only minor changes in the lone-pair spectral region, challenging an interpretation in terms of two interconverting species. A number of alternative hypotheses to explain the results are put forward and discussed. Although the spectra can be explained by various contributions from these hypotheses, we here emphasize the interpretation that the line shape of each component changes dramatically when approaching lower temperatures, where, in particular, the peak assigned to the proposed disordered component would become more symmetrical as vibrational interference becomes more important.

Time-resolved resonant soft x-ray diffraction with free-electron lasers: Femtosecond dynamics across the Verwey transition in magnetite

Resonant soft x-ray diffraction (RSXD) with femtosecond (fs) time resolution is a powerful tool for disentangling the interplay between different degrees of freedom in strongly correlated electron materials. It allows addressing the coupling of particular degrees of freedom upon an external selective perturbation, e.g., by an optical or infrared laser pulse. Here, we report a time-resolved RSXD experiment from the prototypical correlated electron material magnetite using soft x-ray pulses from the free-electron laser FLASH in Hamburg. We observe ultrafast melting of the charge-orbital order leading to the formation of a transient phase, which has not been observed in equilibrium.

Vacuum space charge effects in sub-picosecond soft X-ray photoemission on a molecular adsorbate layer

Vacuum space charge induced kinetic energy shifts of O 1s and Ru 3d core levels in femtosecond soft X-ray photoemission spectra (PES) have been studied at a free electron laser (FEL) for an oxygen layer on Ru(0001). We fully reproduced the measurements by simulating the in-vacuum expansion of the photoelectrons and demonstrate the space charge contribution of the high-order harmonics in the FEL beam. Employing the same analysis for 400u2009nm pump-X-ray probe PES, we can disentangle the delay dependent Ru 3d energy shifts into effects induced by space charge and by lattice heating from the femtosecond pump pulse.

Near edge x-ray absorption fine structure spectroscopy with x-ray free-electron lasers

We demonstrate the feasibility of Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy on solids by means of femtosecond soft x-ray pulses from a free-electron laser (FEL). Our experiments, carried out at the Free-Electron Laser at Hamburg (FLASH), used a special sample geometry, spectrographic energy dispersion, single shot position-sensitive detection and a data normalization procedure that eliminates the severe fluctuations of the incident intensity in space and photon energy. As an example we recorded the {sup 3}D{sub 1} N{sub 4,5}-edge absorption resonance of La{sup 3+}-ions in LaMnO{sub 3}. Our study opens the door for x-ray absorption measurements on future x-ray FEL facilities.

Principles of femtosecond X-ray/optical cross-correlation with X-ray induced transient optical reflectivity in solids

The discovery of ultrafast X-ray induced optical reflectivity changes enabled the development of X-ray/optical cross correlation techniques at X-ray free electron lasers worldwide. We have now linked through experiment and theory the fundamental excitation and relaxation steps with the transient optical properties in finite solid samples. Therefore, we gain a thorough interpretation and an optimized detection scheme of X-ray induced changes to the refractive index and the X-ray/optical cross correlation response.

Measurement of the predicted asymmetric closing behaviour of the band gap of silicon using x-ray absorption and emission spectroscopy

We experimentally observe the theoretically anticipated but so far unverified asymmetric band gap closing for the prototypical semiconductor silicon from room temperature up to the melting point. The shift of the valence band maximum contributes more than 60% to the band gap closing in comparison to the shift of the conduction band minimum. Since we determine the temperature-dependent band edge positions with x-ray absorption and x-ray emission spectroscopy, our analysis also includes electron–phonon coupling features and processes inherent to core-level spectroscopies, like the multi-electron screening response.

The role of space charge in spin-resolved photoemission experiments

Spin-resolved photoemission is one of the most direct ways of measuring the magnetization of a ferromagnet. If all valence band electrons contribute, the measured average spin polarization is proportional to the magnetization. This is even the case if electronic excitations are present, and thus is of particular interest for studying the response of the magnetization to a pump laser pulse. Here, we demonstrate the feasibility of ultrafast spin-resolved photoemission using free electron laser (FEL) radiation and investigate the effect of space charge on the detected spin polarization. The sample is exposed to the radiation of the FEL FLASH in Hamburg. Surprisingly, the measured spin polarization depends on the fluence of the FEL radiation: a higher FEL fluence reduces the measured spin polarization. Space-charge simulations can explain this effect. These findings have consequences for future spin-polarized photoemission experiments using pulsed photon sources.

Anti-Stokes resonant x-ray Raman scattering for atom specific and excited state selective dynamics

Ultrafast electronic and structural dynamics of matter govern rate and selectivity of chemical reactions, as well as phase transitions and efficient switching in functional materials. Since x-rays determine electronic and structural properties with elemental, chemical, orbital and magnetic selectivity, short pulse x-ray sources have become central enablers of ultrafast science. Despite of these strengths, ultrafast x-rays have been poor at picking up excited state moieties from the unexcited ones. With time-resolved anti-Stokes resonant x-ray Raman scattering (AS-RXRS) performed at the LCLS, and ab initio theory we establish background free excited state selectivity in addition to the elemental, chemical, orbital and magnetic selectivity of x-rays. This unparalleled selectivity extracts low concentration excited state species along the pathway of photo induced ligand exchange of Fe(CO)5 in ethanol. Conceptually a full theoretical treatment of all accessible insights to excited state dynamics with AS-RXRS with transform-limited x-ray pulses is given - which will be covered experimentally by upcoming transform-limited x-ray sources. (Less)

Implications of stimulated resonant X-ray scattering for spectroscopy, imaging, and diffraction in the regime from soft to hard X-rays

The ultrahigh peak brilliance available at X-ray free-electron lasers opens the possibility to transfer nonlinear spectroscopic techniques from the optical and infrared into the X-ray regime. Here, we present a conceptual treatment of nonlinear X-ray processes with an emphasis on stimulated resonant X-ray scattering as well as a quantitative estimate for the scaling of stimulated X-ray scattering cross sections. These considerations provide the order of magnitude for the required X-ray intensities to experimentally observe stimulated resonant X-ray scattering for photon energies ranging from the extreme ultraviolet to the soft and hard X-ray regimes. At the same time, the regime where stimulated processes can safely be ignored is identified. With this basis, we discuss prospects and implications for spectroscopy, scattering, and imaging experiments at X-ray free-electron lasers.