TY  - JOUR
A1  - Ovsyannikov, Ruslan
A1  - Karlsson, P.
A1  - Lundqvist, M.
A1  - Lupulescu, C.
A1  - Eberhardt, W.
A1  - Föhlisch, Alexander
A1  - Svensson, S.
A1  - Martensson, N.
T1  - Principles and operation of a new type of electron spectrometer - ArTOF
JF  - Journal of electron spectroscopy and related phenomena : the international journal on theoretical and experimental aspects of electron spectroscopy
N2  - A new energy and angular electron analyzer ArTOF (Angular Resolved Time of Flight) is described. The analyzer is based on simultaneous measurement of flight times and angles in an advanced electron lens system. In angular modes the new analyzer combines an increase in transmission by almost three orders of magnitude with improved resolution, in comparison to standard state-of-the-art electron spectrometers. In this report we describe some design principles and we give a review of calibration and alignment procedures necessary for the use of the ArTOF on a synchrotron radiation facility. Our program scripts to handle the large datasets are also discussed. Furthermore we give a broad description of the new research fields that benefit from the use of the ArTOF and give a short summary of the first results of angle resolved photoemission measurement with ArTOF using the single-bunch X-ray pulses from the BESSY II storage ring facility. (C) 2013 Published by Elsevier B.V.
KW  - ARPES
KW  - Time of flight
KW  - Synchrotron
KW  - Electron spectroscopy
Y1  - 2013
U6  - https://doi.org/10.1016/j.elspec.2013.08.005
SN  - 0368-2048
SN  - 1873-2526
VL  - 191
IS  - 12
SP  - 92
EP  - 103
PB  - Elsevier
CY  - Amsterdam
ER  - 
TY  - JOUR
A1  - Kunnus, Kristjan
A1  - Josefsson, Ida
A1  - Schreck, Simon
A1  - Quevedo, Wilson
A1  - Miedema, Piter S.
A1  - Techert, Simone
A1  - de Groot, Frank M. F.
A1  - Odelius, Michael
A1  - Wernet, Philippe
A1  - Föhlisch, Alexander
T1  - From Ligand Fields to Molecular Orbitals: Probing the Local Valence Electronic Structure of Ni2+ in Aqueous Solution with Resonant Inelastic X-ray Scattering
JF  - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry
N2  - Bonding of the Ni2+(aq) complex is investigated with an unprecedented combination of resonant inelastic X-ray scattering (RIXS) measurements and ab initio calculations at the Ni L absorption edge. The spectra directly reflect the relative energies of the ligand-field and charge-transfer valence-excited states. They give element-specific access with atomic resolution to the ground-state electronic structure of the complex and allow quantification of ligand-field strength and 3d-3d electron correlation interactions in the Ni2+(aq) complex. The experimentally determined ligand-field strength is 10Dq = 1.1 eV. This and the Racah parameters characterizing 3d-3d Coulomb interactions B = 0.13 eV and C = 0.42 eV as readily derived from the measured energies match very well with the results from UV-vis spectroscopy. Our results demonstrate how L-edge RIXS can be used to complement existing spectroscopic tools for the investigation of bonding in 3d transition-metal coordination compounds in solution. The ab initio RASPT2 calculation is successfully used to simulate the L-edge RIXS spectra.
Y1  - 2013
U6  - https://doi.org/10.1021/jp4100813
SN  - 1520-6106
VL  - 117
IS  - 51
SP  - 16512
EP  - 16521
PB  - American Chemical Society
CY  - Washington
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  - Könnecke, Rene
A1  - Follath, R.
A1  - Pontius, N.
A1  - Schlappa, J.
A1  - Eggenstein, F.
A1  - Zeschke, T.
A1  - Bischoff, P.
A1  - Schmidt, J. -S.
A1  - Noll, T.
A1  - Trabant, C.
A1  - Schreck, S.
A1  - Wernet, Ph.
A1  - Eisebitt, S.
A1  - Senf, F.
A1  - Schuessler-Langeheine, Christian
A1  - Erko, A.
A1  - Föhlisch, Alexander
T1  - The confocal plane grating spectrometer at BESSY II
JF  - Journal of electron spectroscopy and related phenomena : the international journal on theoretical and experimental aspects of electron spectroscopy
N2  - At BESSY II a confocal plane grating spectrometer for resonant inelastic X-ray scattering (RIXS) is currently under commissioning. The new endstation operates with a source size of 4 x 1 mu m(2) provided by its dedicated beamline. The RIXS-spectrometer covers an energy range from 50 eV to 1000 eV, providing a resolving power E/Delta E of 5000-15,000. The beamline allows full polarization control and gives a photon flux of up to 7 x 10(14) photons/s/0.1 A/0.1%bandwidth by offering a resolving power E/Delta E of 4000-12,000.
KW  - Resonant inelastic X-ray scattering
KW  - Soft X-ray monochromator
KW  - High transmission micro focus beamline
KW  - Plane grating emission spectrometer
Y1  - 2013
U6  - https://doi.org/10.1016/j.elspec.2012.11.003
SN  - 0368-2048
VL  - 188
SP  - 133
EP  - 139
PB  - Elsevier
CY  - Amsterdam
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  - Eschenlohr, Andrea
A1  - Battiato, Marco
A1  - Maldonado, R.
A1  - Pontius, N.
A1  - Kachel, T.
A1  - Holldack, K.
A1  - Mitzner, Rolf
A1  - Föhlisch, Alexander
A1  - Oppeneer, P. M.
A1  - Stamm, C.
T1  - Ultrafast spin transport as key to femtosecond demagnetization
JF  - Nature materials
N2  - Irradiating a ferromagnet with a femtosecond laser pulse is known to induce an ultrafast demagnetization within a few hundred femtoseconds. Here we demonstrate that direct laser irradiation is in fact not essential for ultrafast demagnetization, and that electron cascades caused by hot electron currents accomplish it very efficiently. We optically excite a Au/Ni layered structure in which the 30 nm Au capping layer absorbs the incident laser pump pulse and subsequently use the X-ray magnetic circular dichroism technique to probe the femtosecond demagnetization of the adjacent 15 nm Ni layer. A demagnetization effect corresponding to the scenario in which the laser directly excites the Ni film is observed, but with a slight temporal delay. We explain this unexpected observation by means of the demagnetizing effect of a superdiffusive current of non-equilibrium, non-spin-polarized electrons generated in the Au layer.
Y1  - 2013
U6  - https://doi.org/10.1038/NMAT3546
SN  - 1476-1122
VL  - 12
IS  - 4
SP  - 332
EP  - 336
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  - 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  - 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  - 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  - 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  - 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  - INPR
A1  - Föhlisch, Alexander
A1  - de Groot, F. M. F.
A1  - Odelius, Michael
A1  - Techert, Simone
A1  - Wernet, P.
T1  - Comment on "state-dependent electron delocalization dynamics at the solute-solvent interface: soft-x-ray absorption spectroscopy and lambda b initio calculations"
T2  - Physical review letters
Y1  - 2014
U6  - https://doi.org/10.1103/PhysRevLett.112.129302
SN  - 0031-9007
SN  - 1079-7114
VL  - 112
IS  - 12
PB  - American Physical Society
CY  - College Park
ER  - 
TY  - JOUR
A1  - Miedema, Piter S.
A1  - Wernet, Philippe
A1  - Föhlisch, Alexander
T1  - State-dependent fluorescence yields through the core-valence Coulomb exchange parameter
JF  - Physical review : A, Atomic, molecular, and optical physics
N2  - Total and partial fluorescence yield (PFY) L-edge x-ray absorption spectra differ from the transmission x-ray absorption spectra (XAS) through state-dependent fluorescence yield across the XAS. For 3d(1) to 3d(9) in octahedral symmetry we apply simulations of PFY and XAS and show how the atomic 2p3d Coulomb exchange parameter G(pd) governs the differences in the L-3/(L-2 + L-3) branching ratio between PFY and XAS. G(pd) orders the XAS final states following Hund's rules creating a strong state-dependent fluorescence decay strength variation across the XAS leading to the differences between PFY and XAS.
Y1  - 2014
U6  - https://doi.org/10.1103/PhysRevA.89.052507
SN  - 1050-2947
SN  - 1094-1622
VL  - 89
IS  - 5
PB  - American Physical Society
CY  - College Park
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  - Holldack, Karsten
A1  - Ovsyannikov, Ruslan
A1  - Kuske, P.
A1  - Mueller, R.
A1  - Schaelicke, A.
A1  - Scheer, M.
A1  - Gorgoi, Mihaela
A1  - Kuehn, D.
A1  - Leitner, T.
A1  - Svensson, S.
A1  - Martensson, N.
A1  - Föhlisch, Alexander
T1  - Single bunch X-ray pulses on demand from a multi-bunch synchrotron radiation source
JF  - Nature Communications
N2  - Synchrotron radiation facilities routinely operate in a multi-bunch regime, but applications relying on time-of-flight schemes require single bunch operation. Here we show that pulse picking by resonant excitation in a storage ring creates in addition to the multi-bunch operation a distinct and separable single bunch soft X-ray source. It has variable polarization, a photon flux of up to 10(7)-10(9) ph s(-1)/0.1%BW at purity values of 10(4)-10(2) and a repetition rate of 1.25 MHz. The quasi-resonant excitation of incoherent betatron oscillations of electrons allows horizontal pulse separation at variable (also circular) polarization accessible for both, regular 30 ps pulses and ultrashort pulses of 2-3 ps duration. Combined with a new generation of angularly resolving electron spectrometers this creates unique opportunities for time-resolved photoemission studies as confirmed by time-of-flight spectra. Our pulse picking scheme is particularly suited for surface physics at diffraction-limited light sources promising ultimate spectral resolution.
Y1  - 2014
U6  - https://doi.org/10.1038/ncomms5010
SN  - 2041-1723
VL  - 5
PB  - Nature Publ. Group
CY  - London
ER  - 
TY  - JOUR
A1  - Schreck, Simon
A1  - Pietzsch, Annette
A1  - Kunnus, Kristjan
A1  - Kennedy, Brian
A1  - Quevedo, Wilson
A1  - Miedema, Piter S.
A1  - Wernet, Philippe
A1  - Föhlisch, Alexander
T1  - Dynamics of the OH group and the electronic structure of liquid alcohols
JF  - Structural dynamics
N2  - In resonant inelastic soft x-ray scattering (RIXS) from molecular and liquid systems, the interplay of ground state structural and core-excited state dynamical contributions leads to complex spectral shapes that partially allow for ambiguous interpretations. In this work, we dissect these contributions in oxygen K-edge RIXS from liquid alcohols. We use the scattering into the electronic ground state as an accurate measure of nuclear dynamics in the intermediate core-excited state of the RIXS process. We determine the characteristic time in the core-excited state until nuclear dynamics give a measurable contribution to the RIXS spectral profiles to tau(dyn) = 1.2 +/- 0.8 fs. By detuning the excitation energy below the absorption resonance we reduce the effective scattering time below sdyn, and hence suppress these dynamical contributions to a minimum. From the corresponding RIXS spectra of liquid methanol, we retrieve the "dynamic-free" density of states and find that it is described solely by the electronic states of the free methanol molecule. From this and from the comparison of normal and deuterated methanol, we conclude that the split peak structure found in the lone-pair emission region at non-resonant excitation originates from dynamics in the O-H bond in the core-excited state. We find no evidence that this split peak feature is a signature of distinct ground state structural complexes in liquid methanol. However, we demonstrate how changes in the hydrogen bond coordination within the series of linear alcohols from methanol to hexanol affect the split peak structure in the liquid alcohols. (C) 2014 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.
Y1  - 2014
U6  - https://doi.org/10.1063/1.4897981
SN  - 2329-7778
VL  - 1
IS  - 5
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - JOUR
A1  - Yin, Zhong
A1  - Rajkovic, Ivan
A1  - Kubicek, Katharina
A1  - Quevedo, Wilson
A1  - Pietzsch, Annette
A1  - Wernet, Philippe
A1  - Föhlisch, Alexander
A1  - Techert, Simone
T1  - Probing the Hofmeister effect with ultrafast core-hole spectroscopy
JF  - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry
N2  - In the current work, X-ray emission spectra of aqueous solutions of different inorganic salts within the Hofmeister series are presented. The results reflect the direct interaction of the ions with the water molecules and therefore, reveal general properties of the salt-water interactions. Within the experimental precision a significant effect of the ions on the water structure has been observed but no ordering according to the structure maker/structure breaker concept could be mirrored in the results indicating that the Hofmeister effect if existent may be caused by more complex interactions.
Y1  - 2014
U6  - https://doi.org/10.1021/jp504577a
SN  - 1520-6106
VL  - 118
IS  - 31
SP  - 9398
EP  - 9403
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - GEN
A1  - Eschenlohr, Andrea
A1  - Battiato, Mario
A1  - Maldonado, P.
A1  - Pontius, N.
A1  - Kachel, T.
A1  - Holldack, K.
A1  - Mitzner, Rolf
A1  - Föhlisch, Alexander
A1  - Oppeneer, P. M.
A1  - Stamm, Christian
T1  - Optical excitation of thin magnetic layers in multilayer structures Reply
T2  - Nature materials
Y1  - 2014
U6  - https://doi.org/10.1038/nmat3851
SN  - 1476-1122
SN  - 1476-4660
VL  - 13
IS  - 2
SP  - 102
EP  - 103
PB  - Nature Publ. Group
CY  - London
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  - 
TY  - JOUR
A1  - Wernet, Philippe
A1  - Kunnus, Kristjan
A1  - Josefsson, Ida
A1  - Rajkovic, Ivan
A1  - Quevedo, Wilson
A1  - Beye, Martin
A1  - Schreck, Simon
A1  - Gruebel, S.
A1  - Scholz, Mirko
A1  - Nordlund, Dennis
A1  - Zhang, Wenkai
A1  - Hartsock, Robert W.
A1  - Schlotter, William F.
A1  - Turner, Joshua J.
A1  - Kennedy, Brian
A1  - Hennies, Franz
A1  - de Groot, Frank M. F.
A1  - Gaffney, Kelly J.
A1  - Techert, Simone
A1  - Odelius, Michael
A1  - Föhlisch, Alexander
T1  - Orbital-specific mapping of the ligand exchange dynamics of Fe(CO)(5) in solution
JF  - Nature : the international weekly journal of science
N2  - Transition-metal complexes have long attracted interest for fundamental chemical reactivity studies and possible use in solar energy conversion(1,2). Electronic excitation, ligand loss from the metal centre, or a combination of both, creates changes in charge and spin density at the metal site(3-11) that need to be controlled to optimize complexes for photocatalytic hydrogen production(8) and selective carbon-hydrogen bond activation(9-11). An understanding at the molecular level of how transition-metal complexes catalyse reactions, and in particular of the role of the short-lived and reactive intermediate states involved, will be critical for such optimization. However, suitable methods for detailed characterization of electronic excited states have been lacking. Here we show, with the use of X-ray laser-based femtosecond-resolution spectroscopy and advanced quantum chemical theory to probe the reaction dynamics of the benchmark transition-metal complex Fe(CO)(5) in solution, that the photo-induced removal of CO generates the 16-electron Fe(CO)(4) species, a homogeneous catalyst(12,13) with an electron deficiency at the Fe centre(14,15), in a hitherto unreported excited singlet state that either converts to the triplet ground state or combines with a CO or solvent molecule to regenerate a penta-coordinated Fe species on a sub-picosecond timescale. This finding, which resolves the debate about the relative importance of different spin channels in the photochemistry of Fe(CO)(5) (refs 4, 16-20), was made possible by the ability of femtosecond X-ray spectroscopy to probe frontier-orbital interactions with atom specificity. We expect the method to be broadly applicable in the chemical sciences, and to complement approaches that probe structural dynamics in ultrafast processes.
Y1  - 2015
U6  - https://doi.org/10.1038/nature14296
SN  - 0028-0836
SN  - 1476-4687
VL  - 520
IS  - 7545
SP  - 78
EP  - 81
PB  - Nature Publ. Group
CY  - London
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  - Förster, Daniel F.
A1  - Lindenau, Bernd
A1  - Leyendecker, Marko
A1  - Janssen, Franz
A1  - Winkler, Carsten
A1  - Schumann, Frank O.
A1  - Kirschner, Juergen
A1  - Holldack, Karsten
A1  - Föhlisch, Alexander
T1  - Phase-locked MHz pulse selector for x-ray sources
JF  - Optics letters : a publication of the Optical Society of America
N2  - Picosecond x-ray pulses are extracted with a phase-locked x-ray pulse selector at 1.25 MHz repetition rate from the pulse trains of the accelerator-driven multiuser x-ray source BESSY II preserving the peak brilliance at high pulse purity. The system consists of a specially designed in-vacuum chopper wheel rotating with approximate to 1 kHz angular frequency. The wheel is driven in an ultrahigh vacuum and is levitated on magnetic bearings being capable of withstanding high centrifugal forces. Pulses are picked by 1252 high-precision slits of 70 mu m width on the outer rim of the wheel corresponding to a temporal opening window of the chopper of 70 ns. We demonstrate how the electronic phase stabilization of +/- 2 ns together with an arrival time jitter of the individual slits of the same order of magnitude allows us to pick short single bunch x-ray pulses out of a 200 ns ion clearing gap in a multibunch pulse train as emitted from a synchrotron facility at 1.25 MHz repetition rate with a pulse purity below the shot noise detection limit. The approach is applicable to any high-repetition pulsed radiation source, in particular in the x-ray spectral range up to 10 keV. The opening window in a real x-ray beamline, its stability, as well as the limits of mechanical pulse picking techniques in the MHz range are discussed. (C) 2015 Optical Society of America
Y1  - 2015
U6  - https://doi.org/10.1364/OL.40.002265
SN  - 0146-9592
SN  - 1539-4794
VL  - 40
IS  - 10
SP  - 2265
EP  - 2268
PB  - Optical Society of America
CY  - Washington
ER  - 
TY  - JOUR
A1  - Kunnus, Kristjan
A1  - Schreck, Simon
A1  - Föhlisch, Alexander
T1  - Free-electron laser based resonant inelastic X-ray scattering on molecules and liquids
JF  - Journal of electron spectroscopy and related phenomena : the international journal on theoretical and experimental aspects of electron spectroscopy
N2  - The unprecedented beam properties of free-electron laser based X-ray sources enable novel resonant inelastic X-ray scattering (RIXS) experiments. Femtosecond time-resolved RIXS can be used to follow charge, spin and structural dynamics of dilute solute molecules in solution. Ultrashort X-ray pulses allow probing of highly radiation sensitive states of matter such as the metastable phase of supercooled liquid water. Nonlinear X-ray probes like amplified spontaneous emission and stimulated resonant X-ray scattering provide an enhanced selectivity and sensitivity as well as a path to control radiation damage and increase the photon yields in RIXS experiments. (C) 2015 Elsevier B.V. All rights reserved.
KW  - Free-electron laser
KW  - RIXS
KW  - Pump-probe
KW  - Nonlinear X-ray spectroscopy
KW  - Molecules
KW  - Liquids
Y1  - 2015
U6  - https://doi.org/10.1016/j.elspec.2015.08.012
SN  - 0368-2048
SN  - 1873-2526
VL  - 204
SP  - 345
EP  - 355
PB  - Elsevier
CY  - Amsterdam
ER  - 
TY  - JOUR
A1  - Yin, Zhong
A1  - Rajkovic, Ivan
A1  - Veedu, Sreevidya Thekku
A1  - Deinert, Sascha
A1  - Raiser, Dirk
A1  - Jain, Rohit
A1  - Fukuzawa, Hironobu
A1  - Wada, Shin-ichi
A1  - Quevedo, Wilson
A1  - Kennedy, Brian
A1  - Schreck, Simon
A1  - Pietzsch, Annette
A1  - Wernet, Philippe
A1  - Ueda, Kyoshi
A1  - Föhlisch, Alexander
A1  - Techert, Simone
T1  - Ionic solutions probed by resonant inelastic X-ray scattering
JF  - Zeitschrift für physikalische Chemie : international journal of research in physical chemistry and chemical physics
N2  - X-ray spectroscopy is a powerful tool to study the local charge distribution of chemical systems. Together with the liquid jet it becomes possible to probe chemical systems in their natural environment, the liquid phase. In this work, we present X-ray absorption (XA), X-ray emission (XE) and resonant inelastic X-ray scattering (RIXS) data of pure water and various salt solutions and show the possibilities these methods offer to elucidate the nature of ion-water interaction.
KW  - X-ray Spectroscopy
KW  - XAS
KW  - XES
KW  - RIXS
KW  - Anions
KW  - Cations
KW  - Liquid Jet
KW  - Synchrotron Radiation
Y1  - 2015
U6  - https://doi.org/10.1515/zpch-2015-0610
SN  - 0942-9352
VL  - 229
IS  - 10-12
SP  - 1855
EP  - 1867
PB  - De Gruyter
CY  - Berlin
ER  - 
TY  - JOUR
A1  - Pietzsch, Annette
A1  - Hennies, Franz
A1  - Miedema, Piter S.
A1  - Kennedy, Brian
A1  - Schlappa, Justine
A1  - Schmitt, Thorsten
A1  - Strocov, Vladimir N.
A1  - Föhlisch, Alexander
T1  - Snapshots of the Fluctuating Hydrogen Bond Network in Liquid Water on the Sub-Femtosecond Timescale with Vibrational Resonant Inelastic x-ray Scattering
JF  - Physical review letters
N2  - Liquid water molecules interact strongly with each other, forming a fluctuating hydrogen bond network and thereby giving rise to the anomalous phase diagram of liquid water. Consequently, symmetric and asymmetric water molecules have been found in the picosecond time average with IR and optical Raman spectroscopy. With subnatural linewidth resonant inelastic x-ray scattering (RIXS) at vibrational resolution, we take sub-femtosecond snapshots of the electronic and structural properties of water molecules in the hydrogen bond network. We derive a strong dominance of nonsymmetric molecules in liquid water in contrast to the gas phase on the sub-femtosecond timescale of RIXS and determine the fraction of highly asymmetrically distorted molecules.
Y1  - 2015
U6  - https://doi.org/10.1103/PhysRevLett.114.088302
SN  - 0031-9007
SN  - 1079-7114
VL  - 114
IS  - 8
PB  - American Physical Society
CY  - College Park
ER  - 
TY  - JOUR
A1  - Rubensson, Jan-Erik
A1  - Soderstrom, Johan
A1  - Binggeli, Christian
A1  - Grasjo, Joakim
A1  - Andersson, Johan
A1  - Sathe, Conny
A1  - Hennies, Franz
A1  - Bisogni, Valentina
A1  - Huang, Yaobo
A1  - Olalde, Paul
A1  - Schmitt, Thorsten
A1  - Strocov, Vladimir N.
A1  - Föhlisch, Alexander
A1  - Kennedy, Brian
A1  - Pietzsch, Annette
T1  - Rydberg-Resolved Resonant Inelastic Soft X-Ray Scattering: Dynamics at Core Ionization Thresholds
JF  - Physical review letters
N2  - Resonant inelastic x-ray scattering spectra excited in the immediate vicinity of the core-level ionization thresholds of N-2 have been recorded. Final states of well-resolved symmetry-selected Rydberg series converging to valence-level ionization thresholds with vibrational excitations are observed. The results are well described by a quasi-two-step model which assumes that the excited electron is unaffected by the radiative decay. This threshold dynamics simplifies the interpretation of resonant inelastic x-ray scattering spectra considerably and facilitates characterization of low-energy excited final states in molecular systems.
Y1  - 2015
U6  - https://doi.org/10.1103/PhysRevLett.114.133001
SN  - 0031-9007
SN  - 1079-7114
VL  - 114
IS  - 13
PB  - American Physical Society
CY  - College Park
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  - Eckert, Sebastian
A1  - Beye, Martin
A1  - Pietzsch, Annette
A1  - Quevedo, Wilson
A1  - Hantschmann, Markus
A1  - Ochmann, Miguel
A1  - Ross, Matthew
A1  - Minitti, Michael P.
A1  - Turner, Joshua J.
A1  - Moeller, Stefan P.
A1  - Schlotter, William F.
A1  - Dakovski, Georgi L.
A1  - Khalil, Munira
A1  - Huse, Nils
A1  - Föhlisch, Alexander
T1  - Principles of femtosecond X-ray/optical cross-correlation with X-ray induced transient optical reflectivity in solids
JF  - Applied physics letters
N2  - 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. (C) 2015 AIP Publishing LLC.
Y1  - 2015
U6  - https://doi.org/10.1063/1.4907949
SN  - 0003-6951
SN  - 1077-3118
VL  - 106
IS  - 6
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - JOUR
A1  - Oberg, H.
A1  - Gladh, Jörgen
A1  - Anniyev, Toyli
A1  - Beye, Martin
A1  - Coffee, Ryan
A1  - Föhlisch, Alexander
A1  - Katayama, T.
A1  - Kaya, Sarp
A1  - LaRue, Jerry
A1  - Mogelhoj, Andreas
A1  - Nordlund, Dennis
A1  - Ogasawara, Hirohito
A1  - Schlotter, William F.
A1  - Sellberg, Jonas A.
A1  - Sorgenfrei, Nomi
A1  - Turner, Joshua J.
A1  - Wolf, Martin
A1  - Wurth, W.
A1  - Ostrom, Henrik
A1  - Nilsson, Anders
A1  - Norskov, Jens K.
A1  - Pettersson, Lars G. M.
T1  - Optical laser-induced CO desorption from Ru(0001) monitored with a free-electron X-ray laser: DFT prediction and X-ray confirmation of a precursor state
JF  - Surface science
N2  - We present density functional theory modeling of time-resolved optical pump/X-ray spectroscopic probe data of CO desorption from Ru(0001). The BEEF van der Waals functional predicts a weakly bound state as a precursor to desorption. The optical pump leads to a near-instantaneous (<100 fs) increase of the electronic temperature to nearly 7000 K. The temperature evolution and energy transfer between electrons, substrate phonons and adsorbate is described by the two-temperature model and found to equilibrate on a timescale of a few picoseconds to an elevated local temperature of similar to 2000K. Estimating the free energy based on the computed potential of mean force along the desorption path, we find an entropic barrier to desorption (and by time-reversal also to adsorption). This entropic barrier separates the chemisorbed and precursor states, and becomes significant at the elevated temperature of the experiment (similar to 1.4 eV at 2000 K). Experimental pump-probe X-ray absorption/X-ray emission spectroscopy indicates population of a precursor state to desorption upon laser-excitation of the system (Dell'Angela et al., 2013). Computing spectra along the desorption path confirms the picture of a weakly bound transient state arising from ultrafast heating of the metal substrate. (C) 2015 Elsevier B.V. All rights reserved.
KW  - CO desorption
KW  - Potential of mean force
KW  - Two-temperature model
KW  - Pump-probe
KW  - X-ray spectroscopy
KW  - Density functional theory
Y1  - 2015
U6  - https://doi.org/10.1016/j.susc.2015.03.011
SN  - 0039-6028
SN  - 1879-2758
VL  - 640
SP  - 80
EP  - 88
PB  - Elsevier
CY  - Amsterdam
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  - Beye, Martin
A1  - Öberg, Henrik
A1  - Xin, Hongliang
A1  - Dakovski, Georgi L.
A1  - Föhlisch, Alexander
A1  - Gladh, Jorgen
A1  - Hantschmann, Markus
A1  - Hieke, Florian
A1  - Kaya, Sarp
A1  - Kühn, Danilo
A1  - LaRue, Jerry
A1  - Mercurio, Giuseppe
A1  - Minitti, Michael P.
A1  - Mitra, Ankush
A1  - Moeller, Stefan P.
A1  - Ng, May Ling
A1  - Nilsson, Anders
A1  - Nordlund, Dennis
A1  - Norskov, Jens
A1  - Öström, Henrik
A1  - Ogasawara, Hirohito
A1  - Persson, Mats
A1  - Schlotter, William F.
A1  - Sellberg, Jonas A.
A1  - Wolf, Martin
A1  - Abild-Pedersen, Frank
A1  - Pettersson, Lars G. M.
A1  - Wurth, Wilfried
T1  - Chemical Bond Activation Observed with an X-ray Laser
JF  - The journal of physical chemistry letters
N2  - The concept of bonding and antibonding orbitals is fundamental in chemistry. The population of those orbitals and the energetic difference between the two reflect the strength of the bonding interaction. Weakening the bond is expected to reduce this energetic splitting, but the transient character of bond-activation has so far prohibited direct experimental access. Here we apply time-resolved soft X-ray spectroscopy at a free electron laser to directly observe the decreased bonding antibonding splitting following bond-activation using an ultrashort optical laser pulse.
Y1  - 2016
U6  - https://doi.org/10.1021/acs.jpclett.6b01543
SN  - 1948-7185
VL  - 7
SP  - 3647
EP  - 3651
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Kunnus, Kristjan
A1  - Josefsson, Ida
A1  - Rajkovic, Ivan
A1  - Schreck, Simon
A1  - Quevedo, Wilson
A1  - Beye, Martin
A1  - Grübel, Sebastian
A1  - Scholz, Mirko
A1  - Nordlund, Dennis
A1  - Zhang, Wenkai
A1  - Hartsock, Robert W.
A1  - Gaffney, Kelly J.
A1  - Schlotter, William F.
A1  - Turner, Joshua J.
A1  - Kennedy, Brian
A1  - Hennies, Franz
A1  - Techert, Simone
A1  - Wernet, Philippe
A1  - Odelius, Michael
A1  - Föhlisch, Alexander
T1  - Anti-Stokes resonant x-ray Raman scattering for atom specific and excited state selective dynamics
JF  - NEW JOURNAL OF PHYSICS
N2  - 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.
KW  - ultrafast photochemistry
KW  - excited state selectivity
KW  - anti-Stokes resonant x-ray raman scattering
KW  - free electron lasers
KW  - resonant inelastic x-ray scattering
Y1  - 2016
U6  - https://doi.org/10.1088/1367-2630/18/10/103011
SN  - 1367-2630
VL  - 18
PB  - IOP Publ. Ltd.
CY  - Bristol
ER  - 
TY  - JOUR
A1  - Kunnus, Kristjan
A1  - Zhang, Wenkai
A1  - Delcey, Mickael G.
A1  - Pinjari, Rahul V.
A1  - Miedema, Piter S.
A1  - Schreck, Simon
A1  - Quevedo, Wilson
A1  - Schröder, Henning
A1  - Föhlisch, Alexander
A1  - Gaffney, Kelly J.
A1  - Lundberg, Marcus
A1  - Odelius, Michael
A1  - Wernet, Philippe
T1  - Viewing the Valence Electronic Structure of Ferric and Ferrous Hexacyanide in Solution from the Fe and Cyanide Perspectives
JF  - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry
N2  - The valence-excited states of ferric and ferrous hexacyanide ions in aqueous solution were mapped by resonant inelastic X-ray scattering (RIXS) at the Fe L-2,L-3 and N K edges. Probing of both the central Fe and the ligand N atoms enabled identification of the metal-and ligand-centered excited states, as well as ligand-to-metal and metal-to-ligand charge-transfer excited states. Ab initio calculations utilizing the RASPT2 method were used to simulate the Fe L-2,L-3-edge RIXS spectra and enabled quantification of the covalencies of both occupied and empty orbitals of pi and sigma symmetry. We found that pi back-donation in the ferric complex is smaller than that in the ferrous complex. This is evidenced by the relative amounts of Fe 3d character in the nominally 2 pi CN- molecular orbital of 7% and 9% in ferric and ferrous hexacyanide, respectively. Utilizing the direct sensitivity of Fe L-3-edge RIXS to the Fe 3d character in the occupied molecular orbitals, we also found that the donation interactions are dominated by sigma bonding. The latter was found to be stronger in the ferric complex, with an Fe 3d contribution to the nominally 5 sigma CN- molecular orbitals of 29% compared to 20% in the ferrous complex. These results are consistent with the notion that a higher charge at the central metal atom increases donation and decreases back-donation.
Y1  - 2016
U6  - https://doi.org/10.1021/acs.jpcb.6b04751
SN  - 1520-6106
VL  - 120
SP  - 7182
EP  - 7194
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Kroll, Thomas
A1  - Kern, Jan
A1  - Kubin, Markus
A1  - Ratner, Daniel
A1  - Gul, Sheraz
A1  - Fuller, Franklin D.
A1  - Löchel, Heike
A1  - Krzywinski, Jacek
A1  - Lutman, Alberto
A1  - Ding, Yuantao
A1  - Dakovski, Georgi L.
A1  - Moeller, Stefan
A1  - Turner, Joshua J.
A1  - Alonso-Mori, Roberto
A1  - Nordlund, Dennis L.
A1  - Rehanek, Jens
A1  - Weniger, Christian
A1  - Firsov, Alexander
A1  - Brzhezinskaya, Maria
A1  - Chatterjee, Ruchira
A1  - Lassalle-Kaiser, Benedikt
A1  - Sierra, Raymond G.
A1  - Laksmono, Hartawan
A1  - Hill, Ethan
A1  - Borovik, Andrew S.
A1  - Erko, Alexei
A1  - Föhlisch, Alexander
A1  - Mitzner, Rolf
A1  - Yachandra, Vittal K.
A1  - Yano, Junko
A1  - Wernet, Philippe
A1  - Bergmann, Uwe
T1  - X-ray absorption spectroscopy using a self-seeded soft X-ray free-electron laser
JF  - Optics express : the international electronic journal of optics
N2  - X-ray free electron lasers (XFELs) enable unprecedented new ways to study the electronic structure and dynamics of transition metal systems. L-edge absorption spectroscopy is a powerful technique for such studies and the feasibility of this method at XFELs for solutions and solids has been demonstrated. However, the required x-ray bandwidth is an order of magnitude narrower than that of self-amplified spontaneous emission (SASE), and additional monochromatization is needed. Here we compare L-edge x-ray absorption spectroscopy (XAS) of a prototypical transition metal system based on monochromatizing the SASE radiation of the linac coherent light source (LCLS) with a new technique based on self-seeding of LCLS. We demonstrate how L-edge XAS can be performed using the self-seeding scheme without the need of an additional beam line monochromator. We show how the spectral shape and pulse energy depend on the undulator setup and how this affects the x-ray spectroscopy measurements. (C) 2016 Optical Society of America
Y1  - 2016
U6  - https://doi.org/10.1364/OE.24.022469
SN  - 1094-4087
VL  - 24
SP  - 22469
EP  - 22480
PB  - Optical Society of America
CY  - Washington
ER  - 
TY  - JOUR
A1  - Schick, Daniel
A1  - Le Guyader, Loic
A1  - Pontius, Niko
A1  - Radu, Ilie
A1  - Kachel, Torsten
A1  - Mitzner, Rolf
A1  - Zeschke, Thomas
A1  - Schuessler-Langeheine, Christian
A1  - Föhlisch, Alexander
A1  - Holldack, Karsten
T1  - Analysis of the halo background in femtosecond slicing experiments
JF  - Journal of synchrotron radiation
N2  - The slicing facility FemtoSpeX at BESSY II offers unique opportunities to study photo-induced dynamics on femtosecond time scales by means of X-ray magnetic circular dichroism, resonant and non-resonant X-ray diffraction, and X-ray absorption spectroscopy experiments in the soft X-ray regime. Besides femtosecond X-ray pulses, slicing sources inherently also produce a so-called `halo' background with a different time structure, polarization and pointing. Here a detailed experimental characterization of the halo radiation is presented, and a method is demonstrated for its correct and unambiguous removal from femtosecond time-resolved data using a special laser triggering scheme as well as analytical models. Examples are given for time-resolved measurements with corresponding halo correction, and errors of the relevant physical quantities caused by either neglecting or by applying a simplified model to describe this background are estimated.
KW  - femtosecond slicing
KW  - halo
KW  - pump-probe
KW  - XMCD
KW  - X-ray scattering
Y1  - 2016
U6  - https://doi.org/10.1107/S160057751600401X
SN  - 1600-5775
VL  - 23
SP  - 700
EP  - 711
PB  - International Union of Crystallography
CY  - Chester
ER  - 
TY  - JOUR
A1  - Schreck, Simon
A1  - Pietzsch, Annette
A1  - Kennedy, Brian
A1  - Sathe, Conny
A1  - Miedema, Piter S.
A1  - Techert, Simone
A1  - Strocov, Vladimir N.
A1  - Schmitt, Thorsten
A1  - Hennies, Franz
A1  - Rubensson, Jan-Erik
A1  - Föhlisch, Alexander
T1  - Ground state potential energy surfaces around selected atoms from resonant inelastic x-ray scattering
JF  - Scientific reports
N2  - Thermally driven chemistry as well as materials’ functionality are determined by the potential energy surface of a systems electronic ground state. This makes the potential energy surface a central and powerful concept in physics, chemistry and materials science. However, direct experimental access to the potential energy surface locally around atomic centers and to its long-range structure are lacking. Here we demonstrate how sub-natural linewidth resonant inelastic soft x-ray scattering at vibrational resolution is utilized to determine ground state potential energy surfaces locally and detect long-range changes of the potentials that are driven by local modifications. We show how the general concept is applicable not only to small isolated molecules such as O2 but also to strongly interacting systems such as the hydrogen bond network in liquid water. The weak perturbation to the potential energy surface through hydrogen bonding is observed as a trend towards softening of the ground state potential around the coordinating atom. The instrumental developments in high resolution resonant inelastic soft x-ray scattering are currently accelerating and will enable broad application of the presented approach. With this multidimensional potential energy surfaces that characterize collective phenomena such as (bio)molecular function or high-temperature superconductivity will become accessible in near future.
Y1  - 2016
U6  - https://doi.org/10.1038/srep20054
SN  - 2045-2322
VL  - 6
PB  - Nature Publ. Group
CY  - London
ER  - 
TY  - JOUR
A1  - Eckert, Sebastian
A1  - Miedema, P. S.
A1  - Quevedo, W.
A1  - Fondell, Mattis
A1  - Beye, Martin
A1  - Pietzsch, Annette
A1  - Ross, M.
A1  - Khalil, M.
A1  - Föhlisch, Alexander
T1  - Molecular structures and protonation state of 2-Mercaptopyridine in aqueous solution
JF  - Chemical physics letters
N2  - The speciation of 2-Mercaptopyridine in aqueous solution has been investigated with nitrogen 1s Near Edge X-ray Absorption Fine Structure spectroscopy and time dependent Density Functional Theory. The prevalence of distinct species as a function of the solvent basicity is established. No indications of dimerization towards high concentrations are found. The determination of different molecular structures of 2-Mercaptopyridine in aqueous solution is put into the context of proton-transfer in keto-enol and thione-thiol tautomerisms. (C) 2016 The Authors. Published by Elsevier B.V.
Y1  - 2016
U6  - https://doi.org/10.1016/j.cplett.2016.01.050
SN  - 0009-2614
SN  - 1873-4448
VL  - 647
SP  - 103
EP  - 106
PB  - Elsevier
CY  - Amsterdam
ER  - 
TY  - JOUR
A1  - Schick, Daniel
A1  - Eckert, Sebastian
A1  - Pontius, Niko
A1  - Mitzner, Rolf
A1  - Föhlisch, Alexander
A1  - Holldack, Karsten
A1  - Sorgenfrei, Nomi
T1  - Versatile soft X-ray-optical cross-correlator for ultrafast applications
JF  - Structural dynamics
N2  - We present an X-ray-optical cross-correlator for the soft (> 150 eV) up to the hard X-ray regime based on a molybdenum-silicon superlattice. The cross-correlation is done by probing intensity and position changes of superlattice Bragg peaks caused by photoexcitation of coherent phonons. This approach is applicable for a wide range of X-ray photon energies as well as for a broad range of excitation wavelengths and requires no external fields or changes of temperature. Moreover, the cross-correlator can be employed on a 10 ps or 100 fs time scale featuring up to 50% total X-ray reflectivity and transient signal changes of more than 20%. (C) 2016 Author(s).
Y1  - 2016
U6  - https://doi.org/10.1063/1.4964296
SN  - 2329-7778
VL  - 3
SP  - 054304-1
EP  - 054304-8
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - JOUR
A1  - Kunnus, Kristjan
A1  - Josefsson, I.
A1  - Schreck, Simon Frederik
A1  - Quevedo, W.
A1  - Miedema, P. S.
A1  - Techert, S.
A1  - de Groot, F. M. F.
A1  - Föhlisch, Alexander
A1  - Odelius, M.
A1  - Wernet, Ph.
T1  - Quantifying covalent interactions with resonant inelastic soft X-ray scattering
BT  - case study of Ni2+ aqua complex
JF  - Chemical physics letters
N2  - We analyze the effects of covalent interactions in Ni 2p3d resonant inelastic X-ray scattering (RIXS) spectra from aqueous Ni2+ ions and find that the relative RIXS intensities of ligand-to-metal charge-transfer final states with respect to the ligand-field final states reflect the covalent mixing between Ni 3d and water orbitals. Specifically, the experimental intensity ratio at the Ni L-3-edge allows to determine that the Ni 3d orbitals have on average 5.5% of water character. We propose that 2p3d RIXS at the Ni L-3-edge can be utilized to quantify covalency in Ni complexes without the use of external references or simulations.
KW  - Transition-metal ion
KW  - Aqueous solution
KW  - Covalent interaction
KW  - Resonant inelastic X-ray scattering
KW  - Ligand-field state
KW  - Charge-transfer state
Y1  - 2016
U6  - https://doi.org/10.1016/j.cplett.2016.12.046
SN  - 0009-2614
SN  - 1873-4448
VL  - 669
SP  - 196
EP  - 201
PB  - Elsevier
CY  - Amsterdam
ER  - 
TY  - JOUR
A1  - Niskanen, Johannes
A1  - Jankala, Kari
A1  - Huttula, Marco
A1  - Föhlisch, Alexander
T1  - QED effects in 1s and 2s single and double ionization potentials of the noble gases
JF  - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr
N2  - We present calculations on the quantum electrodynamics (QED) effects in 1s and 2s single and double ionization potentials of noble gases from Ne to Rn as perturbations on relativistic four-component Dirac-Fock wavefunctions. The most dominant effect originates from the self-energy of the core-electron that yields corrections of similar order as the transverse interaction. For 1s ionization potentials, a match within few eV against the known experimental values is obtained, and our work reveals considerable QED effects in the photoelectron binding energies across the periodic table-most strikingly even for Ne. We perform power-law fits for the corrections as a function of Z and interpolate the QED correction of similar to-0.55 eV for S1s. Due to this, the K-edge electron spectra of the third row and below need QED for a match in the absolute energy when using state-of-the-art instrumentation. Published by AIP Publishing.
Y1  - 2017
U6  - https://doi.org/10.1063/1.4979991
SN  - 0021-9606
SN  - 1089-7690
VL  - 146
SP  - 1443
EP  - 1450
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - JOUR
A1  - Niskanen, Johannes
A1  - Sahle, Christoph J.
A1  - Gilmore, Keith
A1  - Uhlig, Frank
A1  - Smiatek, Jens
A1  - Föhlisch, Alexander
T1  - Disentangling structural information from core-level excitation spectra
JF  - Physical review : E, Statistical, nonlinear and soft matter physics
N2  - Core-level spectra of liquids can be difficult to interpret due to the presence of a range of local environments. We present computational methods for investigating core-level spectra based on the idea that both local structural parameters and the x-ray spectra behave as functions of the local atomic configuration around the absorbing site. We identify correlations between structural parameters and spectral intensities in defined regions of interest, using the oxygen K-edge excitation spectrum of liquid water as a test case. Our results show that this kind of analysis can find the main structure-spectral relationships of ice, liquid water, and supercritical water.
Y1  - 2017
U6  - https://doi.org/10.1103/PhysRevE.96.013319
SN  - 2470-0045
SN  - 2470-0053
VL  - 96
PB  - American Physical Society
CY  - College Park
ER  - 
TY  - JOUR
A1  - Kubin, Markus
A1  - Kern, Jan
A1  - Gul, Sheraz
A1  - Kroll, Thomas
A1  - Chatterjee, Ruchira
A1  - Loechel, Heike
A1  - Fuller, Franklin D.
A1  - Sierra, Raymond G.
A1  - Quevedo, Wilson
A1  - Weniger, Christian
A1  - Rehanek, Jens
A1  - Firsov, Anatoly
A1  - Laksmono, Hartawan
A1  - Weninger, Clemens
A1  - Alonso-Mori, Roberto
A1  - Nordlund, Dennis L.
A1  - Lassalle-Kaiser, Benedikt
A1  - Glownia, James M.
A1  - Krzywinski, Jacek
A1  - Moeller, Stefan
A1  - Turner, Joshua J.
A1  - Minitti, Michael P.
A1  - Dakovski, Georgi L.
A1  - Koroidov, Sergey
A1  - Kawde, Anurag
A1  - Kanady, Jacob S.
A1  - Tsui, Emily Y.
A1  - Suseno, Sandy
A1  - Han, Zhiji
A1  - Hill, Ethan
A1  - Taguchi, Taketo
A1  - Borovik, Andrew S.
A1  - Agapie, Theodor
A1  - Messinger, Johannes
A1  - Erko, Alexei
A1  - Föhlisch, Alexander
A1  - Bergmann, Uwe
A1  - Mitzner, Rolf
A1  - Yachandra, Vittal K.
A1  - Yano, Junko
A1  - Wernet, Philippe
T1  - Soft x-ray absorption spectroscopy of metalloproteins and high-valent metal-complexes at room temperature using free-electron lasers
JF  - Structural dynamics
N2  - X-ray absorption spectroscopy at the L-edge of 3d transition metals provides unique information on the local metal charge and spin states by directly probing 3d-derived molecular orbitals through 2p-3d transitions. However, this soft x-ray technique has been rarely used at synchrotron facilities for mechanistic studies of metalloenzymes due to the difficulties of x-ray-induced sample damage and strong background signals from light elements that can dominate the low metal signal. Here, we combine femtosecond soft x-ray pulses from a free-electron laser with a novel x-ray fluorescence-yield spectrometer to overcome these difficulties. We present L-edge absorption spectra of inorganic high-valent Mn complexes (Mn similar to 6-15 mmol/l) with no visible effects of radiation damage. We also present the first L-edge absorption spectra of the oxygen evolving complex (Mn4CaO5) in Photosystem II (Mn < 1 mmol/l) at room temperature, measured under similar conditions. Our approach opens new ways to study metalloenzymes under functional conditions. (C) 2017 Author(s).
Y1  - 2017
U6  - https://doi.org/10.1063/1.4986627
SN  - 2329-7778
VL  - 4
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - JOUR
A1  - Yin, Zhong
A1  - Inhester, Ludger
A1  - Veedu, Sreevidya Thekku
A1  - Quevedo, Wilson
A1  - Pietzsch, Annette
A1  - Wernet, Philippe
A1  - Groenhof, Gerrit
A1  - Föhlisch, Alexander
A1  - Grubmueller, Helmut
A1  - Techert, Simone
T1  - Cationic and Anionic Impact on the Electronic Structure of Liquid Water
JF  - The journal of physical chemistry letters
N2  - Hydration shells around ions are crucial for many fundamental biological and chemical processes. Their local physicochemical properties are quite different from those of bulk water and hard to probe experimentally. We address this problem by combining soft X-ray spectroscopy using a liquid jet and molecular dynamics (MD) simulations together with ab initio electronic structure calculations to elucidate the water ion interaction in a MgCl2 solution at the molecular level. Our results reveal that salt ions mainly affect the electronic properties of water molecules in close vicinity and that the oxygen K-edge X-ray emission spectrum of water molecules in the first solvation shell differs significantly from that of bulk water. Ion-specific effects are identified by fingerprint features in the water X-ray emission spectra. While Mg2+ ions cause a bathochromic shift of the water lone pair orbital, the 3p orbital of the Cl- ions causes an additional peak in the water emission spectrum at around 528 eV.
Y1  - 2017
U6  - https://doi.org/10.1021/acs.jpclett.7b01392
SN  - 1948-7185
VL  - 8
SP  - 3759
EP  - 3764
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Thielemann-Kühn, Nele
A1  - Schick, Daniel
A1  - Pontius, Niko
A1  - Trabant, Christoph
A1  - Mitzner, Rolf
A1  - Holldack, Karsten
A1  - Zabel, Hartmut
A1  - Föhlisch, Alexander
A1  - Schuessler-Langeheine, Christian
T1  - Ultrafast and Energy-Efficient Quenching of Spin Order: Antiferromagnetism Beats Ferromagnetism
JF  - Physical review letters
N2  - By comparing femtosecond laser pulse induced ferro- and antiferromagnetic dynamics in one and the same material-metallic dysprosium-we show both to behave fundamentally different. Antiferromagnetic order is considerably faster and much more efficiently reduced by optical excitation than its ferromagnetic counterpart. We assign the fast and extremely efficient process in the antiferromagnet to an interatomic transfer of angular momentum within the spin system. Our findings imply that this angular momentum transfer channel is effective in other magnetic metals with nonparallel spin alignment. They also point out a possible route towards energy-efficient spin manipulation for magnetic devices.
Y1  - 2017
U6  - https://doi.org/10.1103/PhysRevLett.119.197202
SN  - 0031-9007
SN  - 1079-7114
VL  - 119
PB  - American Physical Society
CY  - College Park
ER  - 
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  - 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  - Vaz da Cruz, Vinicius
A1  - Ertan, Emelie
A1  - Couto, Rafael C.
A1  - Eckert, Sebastian
A1  - Fondell, Mattis
A1  - Dantz, Marcus
A1  - Kennedy, Brian
A1  - Schmitt, Thorsten
A1  - Pietzsch, Annette
A1  - Guimaraes, Freddy F.
A1  - Ågren, Hans
A1  - Odelius, Michael
A1  - Föhlisch, Alexander
A1  - Kimberg, Victor
T1  - A study of the water molecule using frequency control over nuclear dynamics in resonant X-ray scattering
JF  - Physical chemistry, chemical physics : a journal of European Chemical Societies
N2  - In this combined theoretical and experimental study we report a full analysis of the resonant inelastic X-ray scattering (RIXS) spectra of H2O, D2O and HDO. We demonstrate that electronically-elastic RIXS has an inherent capability to map the potential energy surface and to perform vibrational analysis of the electronic ground state in multimode systems. We show that the control and selection of vibrational excitation can be performed by tuning the X-ray frequency across core-excited molecular bands and that this is clearly reflected in the RIXS spectra. Using high level ab initio electronic structure and quantum nuclear wave packet calculations together with high resolution RIXS measurements, we discuss in detail the mode coupling, mode localization and anharmonicity in the studied systems.
Y1  - 2017
U6  - https://doi.org/10.1039/c7cp01215b
SN  - 1463-9076
SN  - 1463-9084
VL  - 19
SP  - 19573
EP  - 19589
PB  - Royal Society of Chemistry
CY  - Cambridge
ER  - 
TY  - JOUR
A1  - Eckert, Sebastian
A1  - Niskanen, Johannes
A1  - Jay, Raphael Martin
A1  - Miedema, Piter S.
A1  - Fondell, Mattis
A1  - Kennedy, Brian
A1  - Quevedo, Wilson
A1  - Iannuzzi, Marcella
A1  - Föhlisch, Alexander
T1  - Valence orbitals and local bond dynamics around N atoms of histidine under X-ray irradiation
JF  - Physical chemistry, chemical physics : a journal of European Chemical Societies
N2  - The valence orbitals of aqueous histidine under basic, neutral and acidic conditions and their X-ray induced transformations have been monitored through N 1s resonant inelastic X-ray scattering. Using density functional ab initio molecular dynamics simulations in the core-hole state within the Z + 1 approximation, core-excitation-induced molecular transformations are quantified. Spectroscopic evidence for a highly directional X-ray-induced local N-H dissociation within the scattering duration is presented for acidic histidine. Our report demonstrates a protonation-state and chemical-environment dependent propensity for a molecular dissociation, which is induced by the absorption of high energy photons. This case study indicates that structural deformations in biomolecules under exposure to ionizing radiation, yielding possible alteration or loss of function, is highly dependent on the physiological state of the molecule upon irradiation.
Y1  - 2017
U6  - https://doi.org/10.1039/c7cp05713j
SN  - 1463-9076
SN  - 1463-9084
VL  - 19
SP  - 32091
EP  - 32098
PB  - Royal Society of Chemistry
CY  - Cambridge
ER  -