TY - JOUR A1 - Wernet, Philippe A1 - Kunnus, Kristjan A1 - Schreck, Simon A1 - Quevedo, Wilson A1 - Kurian, Reshmi A1 - Techert, Simone A1 - de Groot, Frank M. F. A1 - Odelius, Michael A1 - Föhlisch, Alexander T1 - Dissecting local atomic and intermolecular interactions of transition-metal ions in solution with selective X-ray spectroscopy JF - The journal of physical chemistry letters N2 - Determining covalent and charge-transfer contributions to bonding in solution has remained an experimental challenge. Here, the quenching of fluorescence decay channels as expressed in dips in the L-edge X-ray spectra of solvated 3d transition-metal ions and complexes was reported as a probe. With a full set of experimental and theoretical ab initio L-edge X-ray spectra of aqueous Cr3+, including resonant inelastic X-ray scattering, we address covalency and charge transfer for this prototypical transition-metal ion in solution. We dissect local atomic effects from intermolecular interactions and quantify X-ray optical effects. We find no evidence for the asserted ultrafast charge transfer to the solvent and show that the dips are readily explained by X-ray optical effects and local atomic state dependence of the fluorescence yield. Instead, we find, besides ionic interactions, a covalent contribution to the bonding in the aqueous complex of ligand-to-metal charge-transfer character. Y1 - 2012 U6 - https://doi.org/10.1021/jz301486u SN - 1948-7185 VL - 3 IS - 23 SP - 3448 EP - 3453 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Kunnus, Kristjan A1 - Rajkovic, Ivan A1 - Schreck, Simon A1 - Quevedo, Wilson A1 - Eckert, Sebastian A1 - Beye, Martin A1 - Suljoti, Edlira A1 - Weniger, Christian A1 - Kalus, Christian A1 - Gruebel, 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 - Föhlisch, Alexander T1 - A setup for resonant inelastic soft x-ray scattering on liquids at free electron laser light sources JF - Review of scientific instruments : a monthly journal devoted to scientific instruments, apparatus, and techniques N2 - We present a flexible and compact experimental setup that combines an in vacuum liquid jet with an x-ray emission spectrometer to enable static and femtosecond time-resolved resonant inelastic soft x-ray scattering (RIXS) measurements from liquids at free electron laser (FEL) light sources. We demonstrate the feasibility of this type of experiments with the measurements performed at the Linac Coherent Light Source FEL facility. At the FEL we observed changes in the RIXS spectra at high peak fluences which currently sets a limit to maximum attainable count rate at FELs. The setup presented here opens up new possibilities to study the structure and dynamics in liquids. Y1 - 2012 U6 - https://doi.org/10.1063/1.4772685 SN - 0034-6748 VL - 83 IS - 12 PB - American Institute of Physics CY - Melville 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 - Mitzner, Rolf A1 - Rehanek, Jens A1 - Kern, Jan A1 - Gul, Sheraz A1 - Hattne, Johan A1 - Taguchi, Taketo A1 - Alonso-Mori, Roberto A1 - Tran, Rosalie A1 - Weniger, Christian A1 - Schröder, Henning A1 - Quevedo, Wilson A1 - Laksmono, Hartawan A1 - Sierra, Raymond G. A1 - Han, Guangye A1 - Lassalle-Kaiser, Benedikt A1 - Koroidov, Sergey A1 - Kubicek, Katharina A1 - Schreck, Simon A1 - Kunnus, Kristjan A1 - Brzhezinskaya, Maria A1 - Firsov, Alexander A1 - Minitti, Michael P. A1 - Turner, Joshua J. A1 - Möller, Stefan A1 - Sauter, Nicholas K. A1 - Bogan, Michael J. A1 - Nordlund, Dennis A1 - Schlotter, William F. A1 - Messinger, Johannes A1 - Borovik, Andrew S. A1 - Techert, Simone A1 - de Groot, Frank M. F. A1 - Föhlisch, Alexander A1 - Erko, Alexei A1 - Bergmann, Uwe A1 - Yachandra, Vittal K. A1 - Wernet, Philippe A1 - Yano, Junko T1 - L-edge x-ray absorption spectroscopy of dilute systems relevant to metalloproteins using an X-ray free-electron laser JF - The journal of physical chemistry letters N2 - L-edge spectroscopy of 3d transition metals provides important electronic structure information and has been used in many fields. However, the use of this method for studying dilute aqueous systems, such as metalloenzymes, has not been prevalent because of severe radiation damage and the lack of suitable detection systems. Here we present spectra from a dilute Mn aqueous solution using a high-transmission zone-plate spectrometer at the Linac Coherent Light Source (LCLS). The spectrometer has been optimized for discriminating the Mn L-edge signal from the overwhelming 0 K-edge background that arises from water and protein itself, and the ultrashort LCLS X-ray pulses can outrun X-ray induced damage. We show that the deviations of the partial-fluorescence yield-detected spectra from the true absorption can be well modeled using the state-dependence of the fluorescence yield, and discuss implications for the application of our concept to biological samples. Y1 - 2013 U6 - https://doi.org/10.1021/jz401837f SN - 1948-7185 VL - 4 IS - 21 SP - 3641 EP - 3647 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Meibohm, Jan A1 - Schreck, Simon A1 - Wernet, Philippe T1 - Temperature dependent soft x-ray absorption spectroscopy of liquids JF - Review of scientific instruments : a monthly journal devoted to scientific instruments, apparatus, and techniques N2 - A novel sample holder is introduced which allows for temperature dependent soft x-ray absorption spectroscopy of liquids in transmission mode. The setup is based on sample cells with x-ray transmissive silicon nitride windows. A cooling circuit allows for temperature regulation of the sample liquid between -10 degrees C and +50 degrees C. The setup enables to record soft x-ray absorption spectra of liquids in transmission mode with a temperature resolution of 0.5K and better. Reliability and reproducibility of the spectra are demonstrated by investigating the characteristic temperature-induced changes in the oxygen K-edge x-ray absorption spectrum of liquid water. These are compared to the corresponding changes in the oxygen K-edge spectra from x-ray Raman scattering. (C) 2014 AIP Publishing LLC. Y1 - 2014 U6 - https://doi.org/10.1063/1.4896977 SN - 0034-6748 SN - 1089-7623 VL - 85 IS - 10 PB - American Institute of Physics CY - Melville 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 - 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 - 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 - 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 -