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 - 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 - Jay, Raphael M. A1 - Norell, Jesper A1 - Eckert, Sebastian A1 - Hantschmann, Markus A1 - Beye, Martin A1 - Kennedy, Brian A1 - Quevedo, Wilson A1 - Schlotter, William F. A1 - Dakovski, Georgi L. A1 - Minitti, Michael P. A1 - Hoffmann, Matthias C. A1 - Mitra, Ankush A1 - Moeller, Stefan P. A1 - Nordlund, Dennis A1 - Zhang, Wenkai A1 - Liang, Huiyang W. A1 - Kunnus, Kristian A1 - Kubicek, Katharina A1 - Techert, Simone A. A1 - Lundberg, Marcus A1 - Wernet, Philippe A1 - Gaffney, Kelly A1 - Odelius, Michael A1 - Föhlisch, Alexander T1 - Disentangling Transient Charge Density and Metal-Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering JF - The journal of physical chemistry letters N2 - Soft X-ray spectroscopies are ideal probes of the local valence electronic structure of photocatalytically active metal sites. Here, we apply the selectivity of time resolved resonant inelastic X-ray scattering at the iron L-edge to the transient charge distribution of an optically excited charge-transfer state in aqueous ferricyanide. Through comparison to steady-state spectra and quantum chemical calculations, the coupled effects of valence-shell closing and ligand-hole creation are experimentally and theoretically disentangled and described in terms of orbital occupancy, metal-ligand covalency, and ligand field splitting, thereby extending established steady-state concepts to the excited-state domain. pi-Back-donation is found to be mainly determined by the metal site occupation, whereas the ligand hole instead influences sigma-donation. Our results demonstrate how ultrafast resonant inelastic X-ray scattering can help characterize local charge distributions around catalytic metal centers in short-lived charge-transfer excited states, as a step toward future rationalization and tailoring of photocatalytic capabilities of transition-metal complexes. Y1 - 2018 U6 - https://doi.org/10.1021/acs.jpclett.8b01429 SN - 1948-7185 VL - 9 IS - 12 SP - 3538 EP - 3543 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 - Reifarth, Martin A1 - Bekir, Marek A1 - Bapolisi, Alain M. A1 - Titov, Evgenii A1 - Nusshardt, Fabian A1 - Nowaczyk, Julius A1 - Grigoriev, Dmitry A1 - Sharma, Anjali A1 - Saalfrank, Peter A1 - Santer, Svetlana A1 - Hartlieb, Matthias A1 - Böker, Alexander T1 - A dual pH- and light-responsive spiropyrane-based surfactant BT - investigations on Its switching behavior and remote control over emulsion stability JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition N2 - A cationic surfactant containing a spiropyrane unit is prepared exhibiting a dual-responsive adjustability of its surface-active characteristics. The switching mechanism of the system relies on the reversible conversion of the non-ionic spiropyrane (SP) to a zwitterionic merocyanine (MC) and can be controlled by adjusting the pH value and via light, resulting in a pH-dependent photoactivity: While the compound possesses a pronounced difference in surface activity between both forms under acidic conditions, this behavior is suppressed at a neutral pH level. The underlying switching processes are investigated in detail, and a thermodynamic explanation based on a combination of theoretical and experimental results is provided. This complex stimuli-responsive behavior enables remote-control of colloidal systems. To demonstrate its applicability, the surfactant is utilized for the pH-dependent manipulation of oil-in-water emulsions. KW - Dual-Responsiveness KW - Manipulation of Emulsion Stability KW - Spiropyrane KW - Surfactant KW - Switchable Surfactants KW - pH-Dependent Photoresponsivity Y1 - 2022 U6 - https://doi.org/10.1002/anie.202114687 SN - 1433-7851 SN - 1521-3773 VL - 61 IS - 21 PB - Wiley-VCH CY - Weinheim 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 - Brinkmann, Kai Oliver A1 - Becker, Tim A1 - Zimmermann, Florian A1 - Kreusel, Cedric A1 - Gahlmann, Tobias A1 - Theisen, Manuel A1 - Haeger, Tobias A1 - Olthof, Selina A1 - Tückmantel, Christian A1 - Günster, M. A1 - Maschwitz, Timo A1 - Göbelsmann, Fabian A1 - Koch, Christine A1 - Hertel, Dirk A1 - Caprioglio, Pietro A1 - Peña-Camargo, Francisco A1 - Perdigón-Toro, Lorena A1 - Al-Ashouri, Amran A1 - Merten, Lena A1 - Hinderhofer, Alexander A1 - Gomell, Leonie A1 - Zhang, Siyuan A1 - Schreiber, Frank A1 - Albrecht, Steve A1 - Meerholz, Klaus A1 - Neher, Dieter A1 - Stolterfoht, Martin A1 - Riedl, Thomas T1 - Perovskite-organic tandem solar cells with indium oxide interconnect JF - Nature N2 - Multijunction solar cells can overcome the fundamental efficiency limits of single-junction devices. The bandgap tunability of metal halide perovskite solar cells renders them attractive for multijunction architectures(1). Combinations with silicon and copper indium gallium selenide (CIGS), as well as all-perovskite tandem cells, have been reported(2-5). Meanwhile, narrow-gap non-fullerene acceptors have unlocked skyrocketing efficiencies for organic solar cells(6,7). Organic and perovskite semiconductors are an attractive combination, sharing similar processing technologies. Currently, perovskite-organic tandems show subpar efficiencies and are limited by the low open-circuit voltage (V-oc) of wide-gap perovskite cells(8) and losses introduced by the interconnect between the subcells(9,10). Here we demonstrate perovskite-organic tandem cells with an efficiency of 24.0 per cent (certified 23.1 per cent) and a high V-oc of 2.15 volts. Optimized charge extraction layers afford perovskite subcells with an outstanding combination of high V-oc and fill factor. The organic subcells provide a high external quantum efficiency in the near-infrared and, in contrast to paradigmatic concerns about limited photostability of non-fullerene cells(11), show an outstanding operational stability if excitons are predominantly generated on the non-fullerene acceptor, which is the case in our tandems. The subcells are connected by an ultrathin (approximately 1.5 nanometres) metal-like indium oxide layer with unprecedented low optical/electrical losses. This work sets a milestone for perovskite-organic tandems, which outperform the best p-i-n perovskite single junctions(12) and are on a par with perovskite-CIGS and all-perovskite multijunctions(13). Y1 - 2022 U6 - https://doi.org/10.1038/s41586-022-04455-0 SN - 0028-0836 SN - 1476-4687 VL - 604 IS - 7905 SP - 280 EP - 286 PB - Nature Research CY - Berlin ER - TY - JOUR A1 - Toala, Jesús Alberto A1 - Oskinova, Lidia M. A1 - Hamann, Wolf-Rainer A1 - Ignace, Richard A1 - Sander, Andreas Alexander Christoph A1 - Shenar, Tomer A1 - Todt, Helge Tobias A1 - Chu, Y. -H. A1 - Guerrero, Martin A. A1 - Hainich, Rainer A1 - Torrejon, Jose Miguel T1 - On the Apparent Absence of Wolf-Rayet plus Neutron Star Systems BT - the Curious Case of WR124 JF - The astrophysical journal : an international review of spectroscopy and astronomical physics ; Part 2, Letters N2 - Among the different types of massive stars in advanced evolutionary stages is the enigmatic WN8h type. There are only a few Wolf-Rayet (WR) stars with this spectral type in our Galaxy. It has long been suggested that WN8h-type stars are the products of binary evolution that may harbor neutron stars (NS). One of the most intriguing WN8h stars is the runaway WR 124 surrounded by its magnificent nebula M1-67. We test the presence of an accreting NS companion in WR 124 using similar to 100 ks long observations by the Chandra X-ray observatory. The hard X-ray emission from WR 124 with a luminosity of L-X similar to 10(31) erg s(-1) is marginally detected. We use the non-local thermodynamic equilibrium stellar atmosphere code PoWR to estimate the WR wind opacity to the X-rays. The wind of a WN8-type star is effectively opaque for X-rays, hence the low X-ray luminosity of WR 124 does not rule out the presence of an embedded compact object. We suggest that, in general, high-opacity WR winds could prevent X-ray detections of embedded NS, and be an explanation for the apparent lack of WR+NS systems. KW - circumstellar matter KW - ISM: jets and outflows KW - stars: massive KW - stars: evolution KW - stars: neutron KW - stars: Wolf-Rayet Y1 - 2018 U6 - https://doi.org/10.3847/2041-8213/aaf39d SN - 2041-8205 SN - 2041-8213 VL - 869 IS - 1 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Steinke, Martin A1 - Oskinova, Lidia M. A1 - Hamann, Wolf-Rainer A1 - Sander, Andreas Alexander Christoph A1 - Liermann, A. A1 - Todt, Helge Tobias T1 - Analysis of the WN star WR102c, its WR nebula, and the associated cluster of massive stars in the Sickle Nebula JF - Tectonophysics : international journal of geotectonics and the geology and physics of the interior of the earth N2 - Context. The massive Wolf-Rayet type star WR102c is located near the Quintuplet Cluster, one of the three massive star clusters in the Galactic centre region. Previous studies indicated that WR102c may have a dusty circumstellar nebula and is among the main ionising sources of the Sickle Nebula associated with the Quintuplet Cluster. Aims. The goals of our study are to derive the stellar parameters of WR102c from the analysis of its spectrum and to investigate its stellar and nebular environment. Methods. We obtained observations with the ESO VLT integral field spectrograph SINFONI in the K-band, extracted the stellar spectra, and analysed them by means of stellar atmosphere models. Results. Our new analysis supersedes the results previously reported for WR102c. We significantly decrease its bolometric luminosity and hydrogen content. We detect four early OB type stars close to WR102c. These stars have radial velocities similar to that of WR102c. We suggest that together with WR102c these stars belong to a distinct star cluster with a total mass of similar to 1000 M-circle dot. We identify a new WR nebula around WR102c in the SINFONI map of the di ff use Br gamma emission and in the HST Pa ff images. The Br gamma line at di ff erent locations is not significantly broadened and similar to the width of nebular emission elsewhere in the H i i region around WR102c. Conclusions. The massive star WR102c located in the Galactic centre region resides in a star cluster containing additional early-type stars. The stellar parameters of WR102c are typical for hydrogen-free WN6 stars. We identify a nebula surrounding WR102c that has a morphology similar to other nebulae around hydrogen-free WR stars, and propose that the formation of this nebula is linked to interaction of the fast stellar wind with the matter ejected at a previous evolutionary stage of WR102c. KW - stars: early-type KW - stars: individual: WR 102c KW - stars: Wolf KW - Rayet KW - Galaxy: center KW - HII regions KW - infrared: stars Y1 - 2016 U6 - https://doi.org/10.1051/0004-6361/201527692 SN - 1432-0746 VL - 588 PB - EDP Sciences CY - Les Ulis ER -