TY  - JOUR
A1  - Ahnen, M. L.
A1  - Ansoldi, S.
A1  - Antonelli, L. A.
A1  - Antoranz, P.
A1  - Babic, A.
A1  - Banerjee, B.
A1  - Bangale, P.
A1  - de Almeida, U. Barres
A1  - Barrio, J. A.
A1  - Gonzalez, J. Becerra
A1  - Bednarek, W.
A1  - Bernardini, E.
A1  - Berti, A.
A1  - Biasuzzi, B.
A1  - Biland, A.
A1  - Blanch, O.
A1  - Bonnefoy, S.
A1  - Bonnoli, G.
A1  - Borracci, F.
A1  - Bretz, T.
A1  - Buson, S.
A1  - Carosi, A.
A1  - Chatterjee, A.
A1  - Clavero, R.
A1  - Colin, P.
A1  - Colombo, E.
A1  - Contreras, J. L.
A1  - Cortina, J.
A1  - Covino, S.
A1  - Da Vela, P.
A1  - Dazzi, F.
A1  - De Angelis, A.
A1  - De Lotto, B.
A1  - Wilhelmi, E. de Ona
A1  - Di Pierro, F.
A1  - Doert, M.
A1  - Dominguez, A.
A1  - Prester, D. Dominis
A1  - Dorner, D.
A1  - Doro, M.
A1  - Einecke, S.
A1  - Glawion, D. Eisenacher
A1  - Elsaesser, D.
A1  - Engelkemeier, M.
A1  - Ramazani, V. Fallah
A1  - Fernandez-Barral, A.
A1  - Fidalgo, D.
A1  - Fonseca, M. V.
A1  - Font, L.
A1  - Frantzen, K.
A1  - Fruck, C.
A1  - Galindo, D.
A1  - Lopez, R. J. Garcia
A1  - Garczarczyk, M.
A1  - Terrats, D. Garrido
A1  - Gaug, M.
A1  - Giammaria, P.
A1  - Godinovic, N.
A1  - Gonzalez Munoz, A.
A1  - Gora, D.
A1  - Guberman, D.
A1  - Hadasch, D.
A1  - Hahn, A.
A1  - Hanabata, Y.
A1  - Hayashida, M.
A1  - Herrera, J.
A1  - Hose, J.
A1  - Hrupec, D.
A1  - Hughes, G.
A1  - Idec, W.
A1  - Kodani, K.
A1  - Konno, Y.
A1  - Kubo, H.
A1  - Kushida, J.
A1  - La Barbera, A.
A1  - Lelas, D.
A1  - Lindfors, E.
A1  - Lombardi, S.
A1  - Longo, F.
A1  - Lopez, M.
A1  - Lopez-Coto, R.
A1  - Majumdar, P.
A1  - Makariev, M.
A1  - Mallot, K.
A1  - Maneva, G.
A1  - Manganaro, M.
A1  - Mannheim, K.
A1  - Maraschi, L.
A1  - Marcote, B.
A1  - Mariotti, M.
A1  - Martinez, M.
A1  - Mazin, D.
A1  - Menzel, U.
A1  - Miranda, J. M.
A1  - Mirzoyan, R.
A1  - Moralejo, A.
A1  - Moretti, E.
A1  - Nakajima, D.
A1  - Neustroev, V.
A1  - Niedzwiecki, A.
A1  - Rosillo, M. Nievas
A1  - Nilsson, K.
A1  - Nishijima, K.
A1  - Noda, K.
A1  - Nogues, L.
A1  - Overkemping, A.
A1  - Paiano, S.
A1  - Palacio, J.
A1  - Palatiello, M.
A1  - Paneque, D.
A1  - Paoletti, R.
A1  - Paredes, J. M.
A1  - Paredes-Fortuny, X.
A1  - Pedaletti, G.
A1  - Peresano, M.
A1  - Perri, L.
A1  - Persic, M.
A1  - Poutanen, J.
A1  - Moroni, P. G. Prada
A1  - Prandini, E.
A1  - Puljak, I.
A1  - Reichardt, I.
A1  - Rhode, W.
A1  - Ribo, M.
A1  - Rico, J.
A1  - Rodriguez Garcia, J.
A1  - Saito, T.
A1  - Satalecka, K.
A1  - Schroder, S.
A1  - Schultz, C.
A1  - Schweizer, T.
A1  - Shore, S. N.
A1  - Sillanpaa, A.
A1  - Sitarek, J.
A1  - Snidaric, I.
A1  - Sobczynska, D.
A1  - Stamerra, A.
A1  - Steinbring, T.
A1  - Strzys, M.
A1  - Suric, T.
A1  - Takalo, L.
A1  - Tavecchio, F.
A1  - Temnikov, P.
A1  - Terzic, T.
A1  - Tescaro, D.
A1  - Teshima, M.
A1  - Thaele, J.
A1  - Torres, D. F.
A1  - Toyama, T.
A1  - Treves, A.
A1  - Vanzo, G.
A1  - Verguilov, V.
A1  - Vovk, I.
A1  - Ward, J. E.
A1  - Will, M.
A1  - Wu, M. H.
A1  - Zanin, R.
A1  - Abeysekara, A. U.
A1  - Archambault, S.
A1  - Archer, A.
A1  - Benbow, W.
A1  - Bird, R.
A1  - Buchovecky, M.
A1  - Buckley, J. H.
A1  - Bugaev, V.
A1  - Connolly, M. P.
A1  - Cui, W.
A1  - Dickinson, H. J.
A1  - Falcone, A.
A1  - Feng, Q.
A1  - Finley, J. P.
A1  - Fleischhack, H.
A1  - Flinders, A.
A1  - Fortson, L.
A1  - Gillanders, G. H.
A1  - Griffin, S.
A1  - Grube, J.
A1  - Huetten, M.
A1  - Hanna, D.
A1  - Holder, J.
A1  - Humensky, T. B.
A1  - Kaaret, P.
A1  - Kar, P.
A1  - Kelley-Hoskins, N.
A1  - Kertzman, M.
A1  - Kieda, D.
A1  - Krause, M.
A1  - Krennrich, F.
A1  - Lang, M. J.
A1  - Maier, G.
A1  - McCann, A.
A1  - Moriarty, P.
A1  - Mukherjee, R.
A1  - Nieto, D.
A1  - Ong, R. A.
A1  - Otte, N.
A1  - Park, N.
A1  - Perkins, J.
A1  - Pichel, A.
A1  - Pohl, M.
A1  - Popkow, A.
A1  - Pueschel, Elisa
A1  - Quinn, J.
A1  - Ragan, K.
A1  - Reynolds, P. T.
A1  - Richards, G. T.
A1  - Roache, E.
A1  - Rovero, A. C.
A1  - Rulten, C.
A1  - Sadeh, I.
A1  - Santander, M.
A1  - Sembroski, G. H.
A1  - Shahinyan, K.
A1  - Telezhinsky, Igor O.
A1  - Tucci, J. V.
A1  - Tyler, J.
A1  - Wakely, S. P.
A1  - Weinstein, A.
A1  - Wilcox, P.
A1  - Wilhelm, Alina
A1  - Williams, D. A.
A1  - Zitzer, B.
A1  - Razzaque, S.
A1  - Villata, M.
A1  - Raiteri, C. M.
A1  - Aller, H. D.
A1  - Aller, M. F.
A1  - Larionov, V. M.
A1  - Arkharov, A. A.
A1  - Blinov, D. A.
A1  - Efimova, N. V.
A1  - Grishina, T. S.
A1  - Hagen-Thorn, V. A.
A1  - Kopatskaya, E. N.
A1  - Larionova, L. V.
A1  - Larionova, E. G.
A1  - Morozova, D. A.
A1  - Troitsky, I. S.
A1  - Ligustri, R.
A1  - Calcidese, P.
A1  - Berdyugin, A.
A1  - Kurtanidze, O. M.
A1  - Nikolashvili, M. G.
A1  - Kimeridze, G. N.
A1  - Sigua, L. A.
A1  - Kurtanidze, S. O.
A1  - Chigladze, R. A.
A1  - Chen, W. P.
A1  - Koptelova, E.
A1  - Sakamoto, T.
A1  - Sadun, A. C.
A1  - Moody, J. W.
A1  - Pace, C.
A1  - Pearson, R.
A1  - Yatsu, Y.
A1  - Mori, Y.
A1  - Carraminyana, A.
A1  - Carrasco, L.
A1  - de la Fuente, E.
A1  - Norris, J. P.
A1  - Smith, P. S.
A1  - Wehrle, A.
A1  - Gurwell, M. A.
A1  - Zook, A.
A1  - Pagani, C.
A1  - Perri, M.
A1  - Capalbi, M.
A1  - Cesarini, A.
A1  - Krimm, H. A.
A1  - Kovalev, Y. Y.
A1  - Kovalev, Yu. A.
A1  - Ros, E.
A1  - Pushkarev, A. B.
A1  - Lister, M. L.
A1  - Sokolovsky, K. V.
A1  - Kadler, M.
A1  - Piner, G.
A1  - Lahteenmaki, A.
A1  - Tornikoski, M.
A1  - Angelakis, E.
A1  - Krichbaum, T. P.
A1  - Nestoras, I.
A1  - Fuhrmann, L.
A1  - Zensus, J. A.
A1  - Cassaro, P.
A1  - Orlati, A.
A1  - Maccaferri, G.
A1  - Leto, P.
A1  - Giroletti, M.
A1  - Richards, J. L.
A1  - Max-Moerbeck, W.
A1  - Readhead, A. C. S.
T1  - Multiband variability studies and novel broadband SED modeling of Mrk 501 in 2009
JF  - Astronomy and astrophysics : an international weekly journal
N2  - Aims. We present an extensive study of the BL Lac object Mrk 501 based on a data set collected during the multi-instrument campaign spanning from 2009 March 15 to 2009 August 1, which includes, among other instruments, MAGIC, VERITAS, Whipple 10 m, and Fermi-LAT to cover the gamma-ray range from 0.1 GeV to 20 TeV; RXTE and Swift to cover wavelengths from UV to hard X-rays; and GASP-WEBT, which provides coverage of radio and optical wavelengths. Optical polarization measurements were provided for a fraction of the campaign by the Steward and St. Petersburg observatories. We evaluate the variability of the source and interband correlations, the gamma-ray flaring activity occurring in May 2009, and interpret the results within two synchrotron self-Compton (SSC) scenarios. Methods. The multiband variability observed during the full campaign is addressed in terms of the fractional variability, and the possible correlations are studied by calculating the discrete correlation function for each pair of energy bands where the significance was evaluated with dedicated Monte Carlo simulations. The space of SSC model parameters is probed following a dedicated grid-scan strategy, allowing for a wide range of models to be tested and offering a study of the degeneracy of model-to-data agreement in the individual model parameters, hence providing a less biased interpretation than the "single-curve SSC model adjustment" typically reported in the literature. Results. We find an increase in the fractional variability with energy, while no significant interband correlations of flux changes are found on the basis of the acquired data set. The SSC model grid-scan shows that the flaring activity around May 22 cannot be modeled adequately with a one-zone SSC scenario (using an electron energy distribution with two breaks), while it can be suitably described within a two (independent) zone SSC scenario. Here, one zone is responsible for the quiescent emission from the averaged 4.5-month observing period, while the other one, which is spatially separated from the first, dominates the flaring emission occurring at X-rays and very-high-energy (> 100 GeV, VHE) gamma-rays. The flaring activity from May 1, which coincides with a rotation of the electric vector polarization angle (EVPA), cannot be satisfactorily reproduced by either a one-zone or a two-independent-zone SSC model, yet this is partially affected by the lack of strictly simultaneous observations and the presence of large flux changes on sub-hour timescales (detected at VHE gamma rays). Conclusions. The higher variability in the VHE emission and lack of correlation with the X-ray emission indicate that, at least during the 4.5-month observing campaign in 2009, the highest energy (and most variable) electrons that are responsible for the VHE gamma rays do not make a dominant contribution to the similar to 1 keV emission. Alternatively, there could be a very variable component contributing to the VHE gamma-ray emission in addition to that coming from the SSC scenario. The studies with our dedicated SSC grid-scan show that there is some degeneracy in both the one-zone and the two-zone SSC scenarios probed, with several combinations of model parameters yielding a similar model-to-data agreement, and some parameters better constrained than others. The observed gamma-ray flaring activity, with the EVPA rotation coincident with the first gamma-ray flare, resembles those reported previously for low frequency peaked blazars, hence suggesting that there are many similarities in the flaring mechanisms of blazars with different jet properties.
KW  - BL Lacertae objects: individual: Markarian 501
KW  - methods: data analysis
Y1  - 2017
U6  - https://doi.org/10.1051/0004-6361/201629540
SN  - 1432-0746
VL  - 603
PB  - EDP Sciences
CY  - Les Ulis
ER  - 
TY  - JOUR
A1  - Grott, Matthias
A1  - Knollenberg, J.
A1  - Hamm, M.
A1  - Ogawa, K.
A1  - Jaumann, R.
A1  - Otto, Katharina Alexandra
A1  - Delbo, M.
A1  - Michel, P.
A1  - Biele, J.
A1  - Neumann, W.
A1  - Knapmeyer, M.
A1  - Kuehrt, E.
A1  - Senshu, H.
A1  - Okada, T.
A1  - Helbert, J.
A1  - Maturilli, A.
A1  - Müller, N.
A1  - Hagermann, A.
A1  - Sakatani, N.
A1  - Tanaka, S.
A1  - Arai, T.
A1  - Mottola, S.
A1  - Tachibana, S.
A1  - Pelivan, Ivanka
A1  - Drube, L.
A1  - Vincent, J-B
A1  - Yano, H.
A1  - Pilorget, C.
A1  - Matz, K. D.
A1  - Schmitz, N.
A1  - Koncz, A.
A1  - Schröder, S. E.
A1  - Trauthan, F.
A1  - Schlotterer, M.
A1  - Krause, C.
A1  - Ho, T-M
A1  - Moussi-Soffys, A.
T1  - Low thermal conductivity boulder with high porosity identified on C-type asteroid (162173) Ryugu
JF  - Nature astronomy
N2  - C-type asteroids are among the most pristine objects in the Solar System, but little is known about their interior structure and surface properties. Telescopic thermal infrared observations have so far been interpreted in terms of a regolith-covered surface with low thermal conductivity and particle sizes in the centimetre range. This includes observations of C-type asteroid (162173) Ryugu1,2,3. However, on arrival of the Hayabusa2 spacecraft at Ryugu, a regolith cover of sand- to pebble-sized particles was found to be absent4,5 (R.J. et al., manuscript in preparation). Rather, the surface is largely covered by cobbles and boulders, seemingly incompatible with the remote-sensing infrared observations. Here we report on in situ thermal infrared observations of a boulder on the C-type asteroid Ryugu. We found that the boulder’s thermal inertia was much lower than anticipated based on laboratory measurements of meteorites, and that a surface covered by such low-conductivity boulders would be consistent with remote-sensing observations. Our results furthermore indicate high boulder porosities as well as a low tensile strength in the few hundred kilopascal range. The predicted low tensile strength confirms the suspected observational bias6 in our meteorite collections, as such asteroidal material would be too frail to survive atmospheric entry7.
Y1  - 2020
U6  - https://doi.org/10.1038/s41550-019-0832-x
SN  - 2397-3366
VL  - 3
IS  - 11
SP  - 971
EP  - 976
PB  - Nature Publishing Group
CY  - London
ER  - 
TY  - JOUR
A1  - Wernet, Philippe
A1  - Leitner, T.
A1  - Josefsson, Ida
A1  - Mazza, T.
A1  - Miedema, P. S.
A1  - Schroder, H.
A1  - Beye, Martin
A1  - Kunnus, K.
A1  - Schreck, S.
A1  - Radcliffe, P.
A1  - Dusterer, S.
A1  - Meyer, M.
A1  - Odelius, Michael
A1  - Fohlisch, Alexander
T1  - Communication: Direct evidence for sequential dissociation of gas-phase Fe(CO)(5) via a singlet pathway upon excitation at 266 nm
JF  - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr
N2  - We prove the hitherto hypothesized sequential dissociation of Fe(CO)(5) in the gas phase upon photoexcitation at 266 nm via a singlet pathway with time-resolved valence and core-level photoelectron spectroscopy with an x-ray free-electron laser. Valence photoelectron spectra are used to identify free CO molecules and to determine the time constants of stepwise dissociation to Fe(CO)(4) within the temporal resolution of the experiment and further to Fe(CO)(3) within 3 ps. Fe 3p core-level photoelectron spectra directly reflect the singlet spin state of the Fe center in Fe(CO)(5), Fe(CO)(4), and Fe(CO)(3) showing that the dissociation exclusively occurs along a singlet pathway without triplet-state contribution. Our results are important for assessing intra- and intermolecular relaxation processes in the photodissociation dynamics of the prototypical Fe(CO)(5) complex in the gas phase and in solution, and they establish time-resolved core-level photoelectron spectroscopy as a powerful tool for determining the multiplicity of transition metals in photochemical reactions of coordination complexes. Published by AIP Publishing.
Y1  - 2017
U6  - https://doi.org/10.1063/1.4984774
SN  - 0021-9606
SN  - 1089-7690
VL  - 146
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - JOUR
A1  - Kleyer, Michael
A1  - Schröder-Esselbach, Boris
A1  - Biedermann, Robert
A1  - Rudner, Michael
A1  - Fritzsch, K.
A1  - Kühner, A.
A1  - Poschlod, P.
A1  - Kahmen, S.
A1  - Tackenberg, O.
A1  - Talmon, E.
A1  - Poethke, H.-J.
A1  - Obermaier, E.
A1  - Hein, S.
A1  - Hinsch, M.
A1  - Henle, K.
A1  - Settele, Josef
A1  - Binzenhöfer, Birgit
A1  - Pfeifer, A.
A1  - Kögl, H.
T1  - Freie Beweidung mit geringer Besatzdichte und Fräsen als alternative Verfahren zur Pflege von Magerrasen
Y1  - 2004
SN  - 0341-7026
ER  - 
TY  - JOUR
A1  - Leitner, T.
A1  - Josefsson, Ida
A1  - Mazza, T.
A1  - Miedema, Piter S.
A1  - Schröder, H.
A1  - Beye, Martin
A1  - Kunnus, Kristjan
A1  - Schreck, S.
A1  - Düsterer, Stefan
A1  - Föhlisch, Alexander
A1  - Meyer, M.
A1  - Odelius, Michael
A1  - Wernet, Philippe
T1  - Time-resolved electron spectroscopy for chemical analysis of photodissociation
BT  - Photoelectron spectra of Fe(CO)(5), Fe(CO)(4), and Fe(CO)(3)
JF  - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr
N2  - The prototypical photoinduced dissociation of Fe(CO)(5) in the gas phase is used to test time-resolved x-ray photoelectron spectroscopy for studying photochemical reactions. Upon one-photon excitation at 266 nm, Fe(CO)(5) successively dissociates to Fe(CO)(4) and Fe(CO)(3) along a pathway where both fragments retain the singlet multiplicity of Fe(CO)(5). The x-ray free-electron laser FLASH is used to probe the reaction intermediates Fe(CO)(4) and Fe(CO)(3) with time-resolved valence and core-level photoelectron spectroscopy, and experimental results are interpreted with ab initio quantum chemical calculations. Changes in the valence photoelectron spectra are shown to reflect changes in the valenceorbital interactions upon Fe-CO dissociation, thereby validating fundamental theoretical concepts in Fe-CO bonding. Chemical shifts of CO 3 sigma inner-valence and Fe 3 sigma core-level binding energies are shown to correlate with changes in the coordination number of the Fe center. We interpret this with coordination-dependent charge localization and core-hole screening based on calculated changes in electron densities upon core-hole creation in the final ionic states. This extends the established capabilities of steady-state electron spectroscopy for chemical analysis to time-resolved investigations. It could also serve as a benchmark for howcharge and spin density changes in molecular dissociation and excited-state dynamics are expressed in valence and core-level photoelectron spectroscopy. Published by AIP Publishing.
Y1  - 2018
U6  - https://doi.org/10.1063/1.5035149
SN  - 0021-9606
SN  - 1089-7690
VL  - 149
IS  - 4
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - GEN
A1  - Alsemgeest, Jitse
A1  - Schröder, S.
A1  - Boettger, Ute
A1  - Pavlov, S. G.
A1  - Weber, I.
A1  - Greshake, A.
A1  - Knöfler, H. -R.
A1  - Altenberger, Uwe
A1  - Hübers, H. -W.
T1  - COMBINED RAMAN-LIBS STUDIES ON IRON SULFIDES TO INVESTIGATE THE EFECTS OF THE LIBS PLASMA ON THE MINERAL COMPOSITION.
T2  - Monthly notices of the Royal Astronomical Society
Y1  - 2016
SN  - 1086-9379
SN  - 1945-5100
VL  - 51
SP  - A147
EP  - A147
PB  - Wiley-Blackwell
CY  - Hoboken
ER  - 
TY  - JOUR
A1  - Grott, Matthias
A1  - Knollenberg, J.
A1  - Hamm, M.
A1  - Ogawa, K.
A1  - Jaumann, R.
A1  - Otto, Katharina Alexandra
A1  - Delbo, M.
A1  - Michel, Patrick
A1  - Biele, J.
A1  - Neumann, Wladimir
A1  - Knapmeyer, Martin
A1  - Kührt, E.
A1  - Senshu, H.
A1  - Okada, T.
A1  - Helbert, Jorn
A1  - Maturilli, A.
A1  - Müller, N.
A1  - Hagermann, A.
A1  - Sakatani, Naoya
A1  - Tanaka, S.
A1  - Arai, T.
A1  - Mottola, Stefano
A1  - Tachibana, Shogo
A1  - Pelivan, Ivanka
A1  - Drube, Line
A1  - Vincent, J-B
A1  - Yano, Hajime
A1  - Pilorget, C.
A1  - Matz, K. D.
A1  - Schmitz, N.
A1  - Koncz, A.
A1  - Schröder, Stefan E.
A1  - Trauthan, F.
A1  - Schlotterer, Markus
A1  - Krause, C.
A1  - Ho, T-M
A1  - Moussi-Soffys, A.
T1  - Low thermal conductivity boulder with high porosity identified on C-type asteroid (162173) Ryugu
JF  - Nature astronomy
N2  - C-type asteroids are among the most pristine objects in the Solar System, but little is known about their interior structure and surface properties. Telescopic thermal infrared observations have so far been interpreted in terms of a regolith-covered surface with low thermal conductivity and particle sizes in the centimetre range. This includes observations of C-type asteroid (162173) Ryugu1,2,3. However, on arrival of the Hayabusa2 spacecraft at Ryugu, a regolith cover of sand- to pebble-sized particles was found to be absent4,5 (R.J. et al., manuscript in preparation). Rather, the surface is largely covered by cobbles and boulders, seemingly incompatible with the remote-sensing infrared observations. Here we report on in situ thermal infrared observations of a boulder on the C-type asteroid Ryugu. We found that the boulder’s thermal inertia was much lower than anticipated based on laboratory measurements of meteorites, and that a surface covered by such low-conductivity boulders would be consistent with remote-sensing observations. Our results furthermore indicate high boulder porosities as well as a low tensile strength in the few hundred kilopascal range. The predicted low tensile strength confirms the suspected observational bias6 in our meteorite collections, as such asteroidal material would be too frail to survive atmospheric entry7
Y1  - 2019
U6  - https://doi.org/10.1038/s41550-019-0832-x
SN  - 2397-3366
VL  - 3
IS  - 11
SP  - 971
EP  - 976
PB  - Nature Publishing Group
CY  - London
ER  - 
TY  - JOUR
A1  - Hubrig, Swetlana
A1  - Plachinda, S. I.
A1  - Hünsch, M.
A1  - Schröder, K.-P.
T1  - Search for magnetic fields in late-type giants
Y1  - 1994
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  - Koch, Sabine
A1  - Titze, Karl
A1  - Treuter, S.
A1  - Schröder, M.
A1  - Zimmermann, Ralf B.
A1  - Steinhausen, Hans-Christoph
A1  - Lehmkuhl, Ulrike
A1  - Rauh, Hellgard
T1  - Maternal use of valproate during pregnancy, risk of major malformations, and brain disorder
Y1  - 2000
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  -