@misc{FondellEckertJayetal.2017, author = {Fondell, Mattis and Eckert, Sebastian Oliver and Jay, Raphael Martin and Weniger, Christian and Quevedo, Wilson and Niskanen, Johannes and Kennedy, Brian and Sorgenfrei, Florian and Schick, Daniel and Giangrisostomi, Erika and Ovsyannikov, Ruslan and Adamczyk, Katrin and Huse, Nils and Wernet, Philippe and Mitzner, Rolf and F{\"o}hlisch, Alexander}, title = {Time-resolved soft X-ray absorption spectroscopy in transmission mode on liquids at MHz repetition rates}, series = {Postprints der Universit{\"a}t Potsdam Mathematisch-Naturwissenschaftliche Reihe}, journal = {Postprints der Universit{\"a}t Potsdam Mathematisch-Naturwissenschaftliche Reihe}, number = {780}, issn = {1866-8372}, doi = {10.25932/publishup-43752}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-437529}, pages = {12}, year = {2017}, abstract = {We present a setup combining a liquid flatjet sample delivery and a MHz laser system for time-resolved soft X-ray absorption measurements of liquid samples at the high brilliance undulator beamline UE52-SGM at Bessy II yielding unprecedented statistics in this spectral range. We demonstrate that the efficient detection of transient absorption changes in transmission mode enables the identification of photoexcited species in dilute samples. With iron(II)-trisbipyridine in aqueous solution as a benchmark system, we present absorption measurements at various edges in the soft X-ray regime. In combination with the wavelength tunability of the laser system, the set-up opens up opportunities to study the photochemistry of many systems at low concentrations, relevant to materials sciences, chemistry, and biology.}, language = {en} } @misc{KubinGuoKrolletal.2018, author = {Kubin, Markus and Guo, Meiyuan and Kroll, Thomas and L{\"o}chel, Heike and K{\"a}llman, Erik and Baker, Michael L. and Mitzner, Rolf and Gul, Sheraz and Kern, Jan and F{\"o}hlisch, Alexander and Erko, Alexei and Bergmann, Uwe and Yachandra, Vittal and Yano, Junko and Lundberg, Marcus and Wernet, Philippe}, title = {Probing the oxidation state of transition metal complexes}, series = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe}, journal = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe}, number = {656}, issn = {1866-8372}, doi = {10.25932/publishup-42505}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-425057}, pages = {17}, year = {2018}, abstract = {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.}, language = {en} } @misc{NorellJayHantschmannetal.2018, author = {Norell, Jesper and Jay, Raphael Martin and Hantschmann, Markus and Eckert, Sebastian Oliver and Guo, Meiyuan and Gaffney, Kelly J. and Wernet, Philippe and Lundberg, Marcus and F{\"o}hlisch, Alexander and Odelius, Michael}, title = {Fingerprints of electronic, spin and structural dynamics from resonant inelastic soft X-ray scattering in transient photo-chemical species}, series = {Postprints der Universit{\"a}t Potsdam Mathematisch-Naturwissenschaftliche Reihe}, journal = {Postprints der Universit{\"a}t Potsdam Mathematisch-Naturwissenschaftliche Reihe}, number = {779}, issn = {1866-8372}, doi = {10.25932/publishup-43749}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-437493}, pages = {7243 -- 7253}, year = {2018}, abstract = {We describe how inversion symmetry separation of electronic state manifolds in resonant inelastic soft X-ray scattering (RIXS) can be applied to probe excited-state dynamics with compelling selectivity. In a case study of Fe L-3-edge RIXS in the ferricyanide complex Fe(CN)(6)(3-), we demonstrate with multi-configurational restricted active space spectrum simulations how the information content of RIXS spectral fingerprints can be used to unambiguously separate species of different electronic configurations, spin multiplicities, and structures, with possible involvement in the decay dynamics of photo-excited ligand-to-metal charge-transfer. Specifically, we propose that this could be applied to confirm or reject the presence of a hitherto elusive transient Quartet species. Thus, RIXS offers a particular possibility to settle a recent controversy regarding the decay pathway, and we expect the technique to be similarly applicable in other model systems of photo-induced dynamics.}, language = {en} }