TY - JOUR A1 - Miedema, P. S. A1 - Mitzner, Rolf A1 - Ganschow, S. A1 - Föhlisch, Alexander A1 - Beye, Martin T1 - X-ray spectroscopy on the active ion in laser crystals JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - The active ions in typical laser crystals were studied with Resonant Inelastic X-ray Scattering (RIXS) and Partial Fluorescence Yield X-ray Absorption (PFY-XAS) spectroscopies as solid state model systems for dilute active centers. We analyzed Ti3+ and Cr3+ in alpha-Al2O3:Ti3+ and LiCaAlF6:Cr3+, respectively. The comparison of experimental data with semi-empirical multiplet calculations provides insights into the electronic structure and shows how measured crystal field energies are related across different spectroscopies. Y1 - 2017 U6 - https://doi.org/10.1039/c7cp03026f SN - 1463-9076 SN - 1463-9084 VL - 19 SP - 21800 EP - 21806 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Sellberg, Jonas A. A1 - McQueen, Trevor A. A1 - Laksmono, Hartawan A1 - Schreck, Simon A1 - Beye, Martin A1 - DePonte, Daniel P. A1 - Kennedy, Brian A1 - Nordlund, Dennis A1 - Sierra, Raymond G. A1 - Schlesinger, Daniel A1 - Tokushima, Takashi A1 - Zhovtobriukh, Iurii A1 - Eckert, Sebastian A1 - Segtnan, Vegard H. A1 - Ogasawara, Hirohito A1 - Kubicek, Katharina A1 - Techert, Simone A1 - Bergmann, Uwe A1 - Dakovski, Georgi L. A1 - Schlotter, William F. A1 - Harada, Yoshihisa A1 - Bogan, Michael J. A1 - Wernet, Philippe A1 - Föhlisch, Alexander A1 - Pettersson, Lars G. M. A1 - Nilsson, Anders T1 - X-ray emission spectroscopy of bulk liquid water in "no-man's land" JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr N2 - The structure of bulk liquid water was recently probed by x-ray scattering below the temperature limit of homogeneous nucleation (T-H) of similar to 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 T-H 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 1b(1)' and 1b(1)" 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. (C) 2015 AIP Publishing LLC. Y1 - 2015 U6 - https://doi.org/10.1063/1.4905603 SN - 0021-9606 SN - 1089-7690 VL - 142 IS - 4 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Dell'Angela, Martina A1 - Anniyev, Toyli A1 - Beye, Martin A1 - Coffee, Ryan A1 - Föhlisch, Alexander A1 - Gladh, Jörgen A1 - Kaya, Sarp A1 - Katayama, Tetsuo A1 - Krupin, Oleg A1 - Nilsson, Anders A1 - Nordlund, Dennis A1 - Schlotter, William F. A1 - Sellberg, Jonas A. A1 - Sorgenfrei, Nomi A1 - Turner, Joshua J. A1 - ÖstrÖm, Henrik A1 - Ogasawara, Hirohito A1 - Wolf, Martin A1 - Wurth, Wilfried T1 - Vacuum space charge effects in sub-picosecond soft X-ray photoemission on a molecular adsorbate layer JF - Structural dynamics N2 - 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 400 nm 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. (C) 2015 Author(s). Y1 - 2015 U6 - https://doi.org/10.1063/1.4914892 SN - 2329-7778 VL - 2 IS - 2 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Eckert, Sebastian A1 - Norell, Jesper A1 - Miedema, Piter S. A1 - Beye, Martin A1 - Fondell, Mattis A1 - Quevedo, Wilson A1 - Kennedy, Brian A1 - Hantschmann, Markus A1 - Pietzsch, Annette A1 - van Kuiken, Benjamin A1 - Ross, Matthew A1 - Minitti, Michael P. A1 - Moeller, Stefan P. A1 - Schlotter, William F. A1 - Khalil, Munira A1 - Odelius, Michael A1 - Föhlisch, Alexander T1 - Untersuchung unabhängiger N‐H‐ und N‐C‐Bindungsverformungen auf ultrakurzen Zeitskalen mit resonanter inelastischer Röntgenstreuung JF - Angewandte Chemie N2 - Die Femtosekundendynamik nach resonanten Photoanregungen mit optischen und Röntgenpulsen ermöglicht eine selektive Verformung von chemischen N‐H‐ und N‐C‐Bindungen in 2‐Thiopyridon in wässriger Lösung. Die Untersuchung der orbitalspezifischen elektronischen Struktur und ihrer Dynamik auf ultrakurzen Zeitskalen mit resonanter inelastischer Röntgenstreuung an der N1s‐Resonanz am Synchrotron und dem Freie‐Elektronen‐Laser LCLS in Kombination mit quantenchemischen Multikonfigurationsberechnungen erbringen den direkten Nachweis dieser kontrollierten photoinduzierten Molekülverformungen und ihrer ultrakurzen Zeitskala. KW - Photochemie KW - Protonierung KW - RIXS (resonante inelastische Röntgenstreuung) KW - Selektiver Bindungsbruch KW - Stickstoff Y1 - 2017 U6 - https://doi.org/10.1002/ange.201700239 SN - 1521-3757 SN - 1521-3773 VL - 129 IS - 22 SP - 6184 EP - 6188 ER - TY - JOUR A1 - Katayama, T. A1 - Anniyev, Toyli A1 - Beye, Martin A1 - Coffee, Ryan A1 - Dell'Angela, M. A1 - Föhlisch, Alexander A1 - Gladh, J. A1 - Kaya, S. A1 - Krupin, O. A1 - Nilsson, A. A1 - Nordlund, D. A1 - Schlotter, W. F. A1 - Sellberg, J. A. A1 - Sorgenfrei, Nomi A1 - Turner, J. J. A1 - Wurth, W. A1 - Öström, H. A1 - Ogasawara, H. T1 - Ultrafast soft X-ray emission spectroscopy of surface adsorbates using an X-ray free electron laser JF - Journal of electron spectroscopy and related phenomena : the international journal on theoretical and experimental aspects of electron spectroscopy N2 - We report on an experimental system designed to probe chemical reactions on solid surfaces on a sub-picosecond timescale using soft X-ray emission spectroscopy at the Linac Coherent Light Source (LCLS) free electron laser (FEL) at the SLAC National Accelerator Laboratory. We analyzed the O 1s X-ray emission spectra recorded from atomic oxygen adsorbed on a Ru(0001) surface at a synchrotron beamline (SSRL, BL13-2) and an FEL beamline (LCLS, SXR). We have demonstrated conditions that provide negligible amount of FEL induced damage of the sample. In addition we show that the setup is capable of tracking the temporal evolution of electronic structure during a surface reaction of submonolayer quantities of CO molecules desorbing from the surface. KW - X-ray emission spectroscopy KW - Surface science KW - Free electron laser KW - Ultrafast Y1 - 2013 U6 - https://doi.org/10.1016/j.elspec.2013.03.006 SN - 0368-2048 VL - 187 IS - 1 SP - 9 EP - 14 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Eckert, Sebastian A1 - Norell, Jesper A1 - Miedema, Piter S. A1 - Beye, Martin A1 - Fondell, Mattis A1 - Quevedo, Wilson A1 - Kennedy, Brian A1 - Hantschmann, Markus A1 - Pietzsch, Annette A1 - Van Kuiken, Benjamin E. A1 - Ross, Matthew A1 - Minitti, Michael P. A1 - Moeller, Stefan P. A1 - Schlotter, William F. A1 - Khalil, Munira A1 - Odelius, Michael A1 - Föhlisch, Alexander T1 - Ultrafast Independent N-H and N-C Bond Deformation Investigated with Resonant Inelastic X-Ray Scattering JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition N2 - The femtosecond excited-state dynamics following resonant photoexcitation enable the selective deformation of N-H and N-C chemical bonds in 2-thiopyridone in aqueous solution with optical or X-ray pulses. In combination with multiconfigurational quantum-chemical calculations, the orbital-specific electronic structure and its ultrafast dynamics accessed with resonant inelastic X-ray scattering at the N 1s level using synchrotron radiation and the soft X-ray free-electron laser LCLS provide direct evidence for this controlled photoinduced molecular deformation and its ultrashort time-scale. KW - nitrogen KW - photochemistry KW - protonation KW - RIXS (resonant inelastic X-ray scattering) KW - selective bond cleavage Y1 - 2017 U6 - https://doi.org/10.1002/anie.201700239 SN - 1433-7851 SN - 1521-3773 VL - 56 SP - 6088 EP - 6092 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Pontius, N. A1 - Kachel, T. A1 - Schüssler-Langeheine, C. A1 - Schlotter, W. F. A1 - Beye, Martin A1 - Sorgenfrei, Nomi A1 - Chang, C. F. A1 - Föhlisch, Alexander A1 - Wurth, W. A1 - Metcalf, P. A1 - Leonov, I. A1 - Yaresko, A. A1 - Stojanovic, N. A1 - Berglund, Martin A1 - Guerassimova, N. A1 - Duesterer, S. A1 - Redlin, H. A1 - Duerr, H. A. T1 - Time-resolved resonant soft x-ray diffraction with free-electron lasers femtosecond dynamics across the Verwey transition in magnetite JF - Applied physics letters N2 - 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. Y1 - 2011 U6 - https://doi.org/10.1063/1.3584855 SN - 0003-6951 VL - 98 IS - 18 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Leitner, T. A1 - Josefsson, Ida A1 - Mazza, T. A1 - Miedema, Piter S. A1 - Schröder, H. A1 - Beye, Martin A1 - Kunnus, Kristjan A1 - Schreck, S. A1 - Düsterer, Stefan A1 - Föhlisch, Alexander A1 - Meyer, M. A1 - Odelius, Michael A1 - Wernet, Philippe T1 - Time-resolved electron spectroscopy for chemical analysis of photodissociation BT - Photoelectron spectra of Fe(CO)(5), Fe(CO)(4), and Fe(CO)(3) JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr N2 - The prototypical photoinduced dissociation of Fe(CO)(5) in the gas phase is used to test time-resolved x-ray photoelectron spectroscopy for studying photochemical reactions. Upon one-photon excitation at 266 nm, Fe(CO)(5) successively dissociates to Fe(CO)(4) and Fe(CO)(3) along a pathway where both fragments retain the singlet multiplicity of Fe(CO)(5). The x-ray free-electron laser FLASH is used to probe the reaction intermediates Fe(CO)(4) and Fe(CO)(3) with time-resolved valence and core-level photoelectron spectroscopy, and experimental results are interpreted with ab initio quantum chemical calculations. Changes in the valence photoelectron spectra are shown to reflect changes in the valenceorbital interactions upon Fe-CO dissociation, thereby validating fundamental theoretical concepts in Fe-CO bonding. Chemical shifts of CO 3 sigma inner-valence and Fe 3 sigma core-level binding energies are shown to correlate with changes in the coordination number of the Fe center. We interpret this with coordination-dependent charge localization and core-hole screening based on calculated changes in electron densities upon core-hole creation in the final ionic states. This extends the established capabilities of steady-state electron spectroscopy for chemical analysis to time-resolved investigations. It could also serve as a benchmark for howcharge and spin density changes in molecular dissociation and excited-state dynamics are expressed in valence and core-level photoelectron spectroscopy. Published by AIP Publishing. Y1 - 2018 U6 - https://doi.org/10.1063/1.5035149 SN - 0021-9606 SN - 1089-7690 VL - 149 IS - 4 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Beye, Martin A1 - Wernet, Ph. A1 - Schüßler-Langeheine, Christian A1 - Föhlisch, Alexander T1 - Time resolved resonant inelastic X-ray scattering: a supreme tool to understand dynamics in solids and molecules JF - Journal of electron spectroscopy and related phenomena : the international journal on theoretical and experimental aspects of electron spectroscopy N2 - Dynamics in materials typically involve different degrees of freedom, like charge, lattice, orbital and spin in a complex interplay. Time-resolved resonant inelastic X-ray scattering (RIXS) as a highly selective tool can provide unique insight and follow the details of dynamical processes while resolving symmetries, chemical and charge states, momenta, spin configurations, etc. In this paper, we review examples where the intrinsic scattering duration time is used to study femtosecond phenomena. Free-electron lasers access timescales starting in the sub-ps range through pump-probe methods and synchrotrons study the time scales longer than tens of ps. In these examples, time-resolved resonant inelastic X-ray scattering is applied to solids as well as molecular systems. KW - Resonant inelastic X-ray scattering KW - Ultrafast spectroscopy KW - Phase transitions KW - Molecular dynamics Y1 - 2013 U6 - https://doi.org/10.1016/j.elspec.2013.04.013 SN - 0368-2048 VL - 188 IS - 3 SP - 172 EP - 182 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Miedema, Piter Sybren A1 - Beye, Martin A1 - Koennecke, R. A1 - Schiwietz, Gregor A1 - Föhlisch, Alexander T1 - Thermal evolution of the band edges of 6H-SiC: X-ray methods compared to the optical band gap JF - Journal of electron spectroscopy and related phenomena : the international journal on theoretical and experimental aspects of electron spectroscopy N2 - The band gap of semiconductors like silicon and silicon carbide (SIC) is the key for their device properties. In this research, the band gap of 6H-SiC and its temperature dependence were analyzed with silicon 2p X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS) allowing for a separate analysis of the conduction-band minimum (CBM) and valence-band maximum (VBM) components of the band gap. The temperature-dependent asymmetric band gap shrinking of 6H-SiC was determined with a valence-band slope of +2.45 x 10(-4) eV/K and a conduction-band slope of -1.334 x 10(-4) eV/K. The apparent asymmetry, e.g., that two thirds of the band-gap shrinking with increasing temperature is due to the VBM evolution in 6H-SiC, is similar to the asymmetry obtained for pure silicon before. The overall band gap temperature-dependence determined with XAS and nonresonant XES is compared to temperature-dependent optical studies. The core-excitonic binding energy appearing in the Si 2p XAS is extracted as the main difference. In addition, the energy loss of the onset of the first band in RIXS yields to values similar to the optical band gap over the tested temperature range. (C) 2014 Elsevier B.V. All rights reserved. KW - RIXS KW - XAS KW - XES KW - Semiconductors KW - Silicon carbide Y1 - 2014 U6 - https://doi.org/10.1016/j.elspec.2014.08.003 SN - 0368-2048 SN - 1873-2526 VL - 197 SP - 37 EP - 42 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Miedema, P. S. A1 - Beye, Martin A1 - Koennecke, R. A1 - Schiwietz, G. A1 - Föhlisch, Alexander T1 - The angular- and crystal-momentum transfer through electron-phonon coupling in silicon and silicon-carbide: similarities and differences JF - New journal of physics : the open-access journal for physics N2 - Electron-phonon scattering has been studied for silicon carbide (6H-SiC) with resonant inelastic x-ray scattering at the silicon 2p edge. The observed electron-phonon scattering yields a crystal momentum transfer rate per average phonon in 6H-SiC of 1.8 fs(-1) while it is 0.2 fs(-1) in crystalline silicon. The angular momentum transfer rate per average phonon for 6H-SiC is 0.1 fs(-1), which is much higher than 0.0035 fs(-1) obtained for crystalline silicon in a previous study. The higher electron-phonon scattering rates in 6H-SiC are a result of the larger electron localization at the silicon atoms in 6H-SiC as compared to crystalline silicon. While delocalized valence electrons can screen effectively (part of) the electron-phonon interaction, this effect is suppressed for 6H-SiC in comparison to crystalline silicon. Smaller contributions to the difference in electron-phonon scattering rates between 6H-SiC and silicon arise from the lower atomic mass of carbon versus silicon and the difference in local symmetry. KW - electron-phonon scattering KW - 6H-SiC KW - RIXS Y1 - 2014 U6 - https://doi.org/10.1088/1367-2630/16/9/093056 SN - 1367-2630 VL - 16 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Xin, Hong A1 - LaRue, Jerry A1 - Oberg, Henrik A1 - Beye, Martin A1 - Turner, J. J. A1 - Gladh, Jörgen A1 - Ng, May L. A1 - Sellberg, Jonas A. A1 - Kaya, Sarp A1 - Mercurio, G. A1 - Hieke, F. A1 - Nordlund, Dennis A1 - Schlotter, William F. A1 - Dakovski, Georgi L. A1 - Minitti, Michael P. A1 - Föhlisch, Alexander A1 - Wolf, Martin A1 - Wurth, Wilfried A1 - Ogasawara, Hirohito A1 - Norskov, Jens K. A1 - Ostrom, Henrik A1 - Pettersson, Lars G. M. A1 - Nilsson, Anders A1 - Abild-Pedersen, Frank T1 - Strong Influence of Coadsorbate Interaction on CO Desorption Dynamics on Ru(0001) Probed by Ultrafast X-Ray Spectroscopy and Ab Initio Simulations JF - Physical review letters N2 - We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species. This is supported with the potential of mean force along the CO desorption path obtained from density-functional theory calculations. Charge density distribution and frozen-orbital analysis suggest that the oxygen-induced reduction of the Pauli repulsion, and consequent increase of the dative interaction between the CO 5 sigma and the charged Ru atom, is the electronic origin of the distinct desorption dynamics. Ab initio molecular dynamics simulations of CO desorption from Ru(0001) and oxygen-coadsorbed Ru(0001) provide further insights into the surface bond-breaking process. Y1 - 2015 U6 - https://doi.org/10.1103/PhysRevLett.114.156101 SN - 0031-9007 SN - 1079-7114 VL - 114 IS - 15 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Miedema, Piter S. A1 - Thielemann-Kühn, Nele A1 - Calafell, Irati Alonso A1 - Schüßler-Langeheine, Christian A1 - Beye, Martin T1 - Strain analysis from M-edge resonant inelastic X-ray scattering of nickel oxide films JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - Electronic structure modifications due to strain are an effective method for tailoring nano-scale functional materials. Demonstrated on nickel oxide (NiO) thin films, Resonant Inelastic X-ray Scattering (RIXS) at the transition-metal M-2,M-3-edge is shown to be a powerful tool for measuring the electronic structure modification due to strain in the near-surface region. Analyses from the M-2,M-3-edge RIXS in comparison with dedicated crystal field multiplet calculations show distortions in 40 nm NiO grown on a magnesium oxide (MgO) substrate (NiO/MgO) similar to those caused by surface relaxation of bulk NiO. The films of 20 and 10 nm NiO/MgO show slightly larger differences from bulk NiO. Quantitatively, the NiO/MgO samples all are distorted from perfect octahedral (O-h) symmetry with a tetragonal parameter Ds of about -0.1 eV, very close to the Ds distortion from octahedral (O-h) symmetry parameter of -0.11 eV obtained for the surface-near region from a bulk NiO crystal. Comparing the spectra of a 20 nm film of NiO grown on a 20 nm magnetite (Fe3O4) film on a MgO substrate (NiO/Fe3O4/MgO) with the calculated multiplet analyses, the distortion parameter Ds appears to be closer to zero, showing that the surface-near region of this templated film is less distorted from O-h symmetry than the surface-near region in bulk NiO. Finally, the potential of M-2,M-3-edge RIXS for other investigations of strain on electronic structure is discussed. Y1 - 2019 U6 - https://doi.org/10.1039/c9cp03593a SN - 1463-9076 SN - 1463-9084 VL - 21 IS - 38 SP - 21596 EP - 21602 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Beye, Martin A1 - Schreck, S. A1 - Sorgenfrei, Nomi A1 - Trabant, C. A1 - Pontius, N. A1 - Schüßler-Langeheine, C. A1 - Wurth, W. A1 - Föhlisch, Alexander T1 - Stimulated X-ray emission for materials science JF - Nature : the international weekly journal of science N2 - Resonant inelastic X-ray scattering and X-ray emission spectroscopy can be used to probe the energy and dispersion of the elementary low-energy excitations that govern functionality in matter: vibronic, charge, spin and orbital excitations(1-7). A key drawback of resonant inelastic X-ray scattering has been the need for high photon densities to compensate for fluorescence yields of less than a per cent for soft X-rays(8). Sample damage from the dominant non-radiative decays thus limits the materials to which such techniques can be applied and the spectral resolution that can be obtained. A means of improving the yield is therefore highly desirable. Here we demonstrate stimulated X-ray emission for crystalline silicon at photon densities that are easily achievable with free-electron lasers(9). The stimulated radiative decay of core excited species at the expense of non-radiative processes reduces sample damage and permits narrow-bandwidth detection in the directed beam of stimulated radiation. We deduce how stimulated X-ray emission can be enhanced by several orders of magnitude to provide, with high yield and reduced sample damage, a superior probe for low-energy excitations and their dispersion in matter. This is the first step to bringing nonlinear X-ray physics in the condensed phase from theory(10-16) to application. Y1 - 2013 U6 - https://doi.org/10.1038/nature12449 SN - 0028-0836 VL - 501 IS - 7466 SP - 191 EP - + PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - de Jong, S. A1 - Kukreja, R. A1 - Trabant, C. A1 - Pontius, N. A1 - Chang, C. F. A1 - Kachel, T. A1 - Beye, Martin A1 - Sorgenfrei, Nomi A1 - Back, C. H. A1 - Braeuer, B. A1 - Schlotter, W. F. A1 - Turner, J. J. A1 - Krupin, O. A1 - Doehler, M. A1 - Zhu, D. A1 - Hossain, M. A. A1 - Scherz, A. O. A1 - Fausti, D. A1 - Novelli, F. A1 - Esposito, M. A1 - Lee, W. S. A1 - Chuang, Y. D. A1 - Lu, D. H. A1 - Moore, R. G. A1 - Yi, M. A1 - Trigo, M. A1 - Kirchmann, P. A1 - Pathey, L. A1 - Golden, M. S. A1 - Buchholz, Marcel A1 - Metcalf, P. A1 - Parmigiani, F. A1 - Wurth, W. A1 - Föhlisch, Alexander A1 - Schuessler-Langeheine, Christian A1 - Duerr, H. A. T1 - Speed limit of the insulator-metal transition in magnetite JF - Nature materials N2 - As the oldest known magnetic material, magnetite (Fe3O4) has fascinated mankind for millennia. As the first oxide in which a relationship between electrical conductivity and fluctuating/localized electronic order was shown(1), magnetite represents a model system for understanding correlated oxides in general. Nevertheless, the exact mechanism of the insulator-metal, or Verwey, transition has long remained inaccessible(2-8). Recently, three- Fe- site lattice distortions called trimeronswere identified as the characteristic building blocks of the low-temperature insulating electronically ordered phase(9). Here we investigate the Verwey transition with pump- probe X- ray diffraction and optical reflectivity techniques, and show how trimerons become mobile across the insulator-metal transition. We find this to be a two- step process. After an initial 300 fs destruction of individual trimerons, phase separation occurs on a 1.5 +/- 0.2 ps timescale to yield residual insulating and metallic regions. This work establishes the speed limit for switching in future oxide electronics(10). Y1 - 2013 U6 - https://doi.org/10.1038/NMAT3718 SN - 1476-1122 SN - 1476-4660 VL - 12 IS - 10 SP - 882 EP - 886 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Beye, Martin A1 - Föhlisch, Alexander T1 - Soft X-ray probes of ultrafast dynamics for heterogeneous catalysis JF - Chemical physics : a journal devoted to experimental and theoretical research involving problems of both a chemical and physical nature N2 - Soft X-ray spectroscopy is one of the best tools to directly address the electronic structure, the driving force of chemical reactions. It enables selective studies on sample surfaces to single out reaction centers in heterogeneous catalytic reactions. With core-hole clock methods, specific dynamics are related to the femtosecond life time of a core-hole. Typically, this method is used with photoemission spectroscopy, but advancements in soft X-ray emission techniques render more specific studies possible. With the advent of bright femtosecond pulsed soft X-ray sources, highly selective pump-probe X-ray emission studies are enabled with temporal resolutions down to tens of femtoseconds. This finally allows to study dynamics in the electronic structure of adsorbed reaction centers on the whole range of relevant time scales - closing the gap between kinetic soft X-ray studies and the atto- to femtosecond core-hole clock techniques. KW - Core-hole clock KW - Resonant inelastic X-ray scattering KW - Ultrafast surface science KW - Photoelectron spectroscopy Y1 - 2013 U6 - https://doi.org/10.1016/j.chemphys.2012.03.023 SN - 0301-0104 SN - 1873-4421 VL - 414 IS - 5 SP - 130 EP - 138 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Beye, Martin A1 - Anniyev, Toyli A1 - Coffee, Ryan A1 - Dell'Angela, Martina A1 - Föhlisch, Alexander A1 - Gladh, J. A1 - Katayama, T. A1 - Kaya, S. A1 - Krupin, O. A1 - Mogelhoj, A. A1 - Nilsson, A. A1 - Nordlund, D. A1 - Norskov, J. K. A1 - Oberg, H. A1 - Ogasawara, H. A1 - Pettersson, Lars G. M. A1 - Schlotter, W. F. A1 - Sellberg, J. A. A1 - Sorgenfrei, Nomi A1 - Turner, J. J. A1 - Wolf, M. A1 - Wurth, Wilfried A1 - Ostrom, H. T1 - Selective ultrafast probing of transient hot chemisorbed and precursor States of CO on Ru(0001) JF - Physical review letters N2 - We have studied the femtosecond dynamics following optical laser excitation of CO adsorbed on a Ru surface by monitoring changes in the occupied and unoccupied electronic structure using ultrafast soft x-ray absorption and emission. We recently reported [M. Dell'Angela et al. Science 339, 1302 (2013)] a phonon-mediated transition into a weakly adsorbed precursor state occurring on a time scale of >2 ps prior to desorption. Here we focus on processes within the first picosecond after laser excitation and show that the metal-adsorbate coordination is initially increased due to hot-electron-driven vibrational excitations. This process is faster than, but occurs in parallel with, the transition into the precursor state. With resonant x-ray emission spectroscopy, we probe each of these states selectively and determine the respective transient populations depending on optical laser fluence. Ab initio molecular dynamics simulations of CO adsorbed on Ru(0001) were performed at 1500 and 3000 K providing insight into the desorption process. Y1 - 2013 U6 - https://doi.org/10.1103/PhysRevLett.110.186101 SN - 0031-9007 VL - 110 IS - 18 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Dell'Angela, M. A1 - Anniyev, Toyli A1 - Beye, Martin A1 - Coffee, Ryan A1 - Föhlisch, Alexander A1 - Gladh, J. A1 - Katayama, T. A1 - Kaya, S. A1 - Krupin, O. A1 - LaRue, J. A1 - Mogelhoj, A. A1 - Nordlund, D. A1 - Norskov, J. K. A1 - Oberg, H. A1 - Ogasawara, H. A1 - Ostrom, H. A1 - Pettersson, Lars G. M. A1 - Schlotter, W. F. A1 - Sellberg, J. A. A1 - Sorgenfrei, Nomi A1 - Turner, J. J. A1 - Wolf, M. A1 - Wurth, W. A1 - Nilsson, A. T1 - Real-time observation of surface bond breaking with an X-ray Laser JF - Science N2 - We used the Linac Coherent Light Source free-electron x-ray laser to probe the electronic structure of CO molecules as their chemisorption state on Ru(0001) changes upon exciting the substrate by using a femtosecond optical laser pulse. We observed electronic structure changes that are consistent with a weakening of the CO interaction with the substrate but without notable desorption. A large fraction of the molecules (30%) was trapped in a transient precursor state that would precede desorption. We calculated the free energy of the molecule as a function of the desorption reaction coordinate using density functional theory, including van der Waals interactions. Two distinct adsorption wells-chemisorbed and precursor state separated by an entropy barrier-explain the anomalously high prefactors often observed in desorption of molecules from metals. Y1 - 2013 U6 - https://doi.org/10.1126/science.1231711 SN - 0036-8075 VL - 339 IS - 6125 SP - 1302 EP - 1305 PB - American Assoc. for the Advancement of Science CY - Washington ER - TY - JOUR A1 - Schreck, Simon A1 - Beye, Martin A1 - Sellberg, Jonas A. A1 - McQueen, Trevor A1 - Laksmono, Hartawan A1 - Kennedy, Brian A1 - Eckert, Sebastian A1 - Schlesinger, Daniel A1 - Nordlund, Dennis A1 - Ogasawara, Hirohito A1 - Sierra, Raymond G. A1 - Segtnan, Vegard H. A1 - Kubicek, Katharina A1 - Schlotter, William F. A1 - Dakovski, Georgi L. A1 - Moeller, Stefan P. A1 - Bergmann, Uwe A1 - Techert, Simone A1 - Pettersson, Lars G. M. A1 - Wernet, Philippe A1 - Bogan, Michael J. A1 - Harada, Yoshihisa A1 - Nilsson, Anders A1 - Föhlisch, Alexander T1 - Reabsorption of soft x-ray emission at high x-ray free-electron laserfluences JF - Physical review letters N2 - We report on oxygen K-edge soft x-ray emission spectroscopy from a liquid water jet at the Linac Coherent Light Source. We observe significant changes in the spectral content when tuning over a wide range of incident x-ray fluences. In addition the total emission yield decreases at high fluences. These modifications result from reabsorption of x-ray emission by valence-excited molecules generated by the Auger cascade. Our observations have major implications for future x-ray emission studies at intense x-ray sources. We highlight the importance of the x-ray pulse length with respect to the core-hole lifetime. Y1 - 2014 U6 - https://doi.org/10.1103/PhysRevLett.113.153002 SN - 0031-9007 SN - 1079-7114 VL - 113 IS - 15 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Ostrom, H. A1 - Oberg, H. A1 - Xin, H. A1 - Larue, J. A1 - Beye, Martin A1 - Gladh, J. A1 - Ng, M. L. A1 - Sellberg, J. A. A1 - Kaya, S. A1 - Mercurio, G. A1 - Nordlund, D. A1 - Hantschmann, Markus A1 - Hieke, F. A1 - Kuehn, D. A1 - Schlotter, W. F. A1 - Dakovski, G. L. A1 - Turner, J. J. A1 - Minitti, M. P. A1 - Mitra, A. A1 - Moeller, S. P. A1 - Föhlisch, Alexander A1 - Wolf, M. A1 - Wurth, W. A1 - Persson, Mats A1 - Norskov, J. K. A1 - Abild-Pedersen, Frank A1 - Ogasawara, Hirohito A1 - Pettersson, Lars G. M. A1 - Nilsson, A. T1 - Probing the transition state region in catalytic CO oxidation on Ru JF - Science N2 - Femtosecond x-ray laser pulses are used to probe the carbon monoxide (CO) oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and oxygen (O) on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the OK-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC-O bond lengths close to the transition state (TS). After 1 ps, 10% of the CO populate the TS region, which is consistent with predictions based on a quantum oscillator model. Y1 - 2015 U6 - https://doi.org/10.1126/science.1261747 SN - 0036-8075 SN - 1095-9203 VL - 347 IS - 6225 SP - 978 EP - 982 PB - American Assoc. for the Advancement of Science CY - Washington ER -