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 - Kubin, Markus A1 - Guo, Meiyuan A1 - Kroll, Thomas A1 - Loechel, Heike A1 - Kallman, Erik A1 - Baker, Michael L. A1 - Mitzner, Rolf A1 - Gul, Sheraz A1 - Kern, Jan A1 - Föhlisch, Alexander A1 - Erko, Alexei A1 - Bergmann, Uwe A1 - Yachandra, Vittal A1 - Yano, Junko A1 - Lundberg, Marcus A1 - Wernet, Philippe T1 - Probing the oxidation state of transition metal complexes BT - a case study on how charge and spin densities determine Mn L-edge X-ray absorption energies JF - Chemical science N2 - Transition metals in inorganic systems and metalloproteins can occur in different oxidation states, which makes them ideal redox-active catalysts. To gain a mechanistic understanding of the catalytic reactions, knowledge of the oxidation state of the active metals, ideally in operando, is therefore critical. L-edge X-ray absorption spectroscopy (XAS) is a powerful technique that is frequently used to infer the oxidation state via a distinct blue shift of L-edge absorption energies with increasing oxidation state. A unified description accounting for quantum-chemical notions whereupon oxidation does not occur locally on the metal but on the whole molecule and the basic understanding that L-edge XAS probes the electronic structure locally at the metal has been missing to date. Here we quantify how charge and spin densities change at the metal and throughout the molecule for both redox and core-excitation processes. We explain the origin of the L-edge XAS shift between the high-spin complexes Mn-II(acac)(2) and Mn-III(acac)(3) as representative model systems and use ab initio theory to uncouple effects of oxidation-state changes from geometric effects. The shift reflects an increased electron affinity of Mn-III in the core-excited states compared to the ground state due to a contraction of the Mn 3d shell upon core-excitation with accompanied changes in the classical Coulomb interactions. This new picture quantifies how the metal-centered core hole probes changes in formal oxidation state and encloses and substantiates earlier explanations. The approach is broadly applicable to mechanistic studies of redox-catalytic reactions in molecular systems where charge and spin localization/delocalization determine reaction pathways. Y1 - 2018 U6 - https://doi.org/10.1039/c8sc00550h SN - 2041-6520 SN - 2041-6539 VL - 9 IS - 33 SP - 6813 EP - 6829 PB - Royal Society of Chemistry CY - Cambridge ER - TY - GEN A1 - Kubin, Markus A1 - Guo, Meiyuan A1 - Kroll, Thomas A1 - Löchel, Heike A1 - Källman, Erik A1 - Baker, Michael L. A1 - Mitzner, Rolf A1 - Gul, Sheraz A1 - Kern, Jan A1 - Föhlisch, Alexander A1 - Erko, Alexei A1 - Bergmann, Uwe A1 - Yachandra, Vittal A1 - Yano, Junko A1 - Lundberg, Marcus A1 - Wernet, Philippe T1 - Probing the oxidation state of transition metal complexes BT - a case study on how charge and spin densities determine Mn L-edge X-ray absorption energies T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - Transition metals in inorganic systems and metalloproteins can occur in different oxidation states, which makes them ideal redox-active catalysts. To gain a mechanistic understanding of the catalytic reactions, knowledge of the oxidation state of the active metals, ideally in operando, is therefore critical. L-edge X-ray absorption spectroscopy (XAS) is a powerful technique that is frequently used to infer the oxidation state via a distinct blue shift of L-edge absorption energies with increasing oxidation state. A unified description accounting for quantum-chemical notions whereupon oxidation does not occur locally on the metal but on the whole molecule and the basic understanding that L-edge XAS probes the electronic structure locally at the metal has been missing to date. Here we quantify how charge and spin densities change at the metal and throughout the molecule for both redox and core-excitation processes. We explain the origin of the L-edge XAS shift between the high-spin complexes Mn-II(acac)(2) and Mn-III(acac)(3) as representative model systems and use ab initio theory to uncouple effects of oxidation-state changes from geometric effects. The shift reflects an increased electron affinity of Mn-III in the core-excited states compared to the ground state due to a contraction of the Mn 3d shell upon core-excitation with accompanied changes in the classical Coulomb interactions. This new picture quantifies how the metal-centered core hole probes changes in formal oxidation state and encloses and substantiates earlier explanations. The approach is broadly applicable to mechanistic studies of redox-catalytic reactions in molecular systems where charge and spin localization/delocalization determine reaction pathways. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 656 KW - electronic-structure KW - atomic multiplet KW - water-oxidation KW - iron complexes KW - photosystem-II KW - spectroscopy KW - manganese KW - spectra KW - ligand KW - FE Y1 - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-425057 SN - 1866-8372 IS - 656 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 -