TY - JOUR A1 - Kunnus, Kristjan A1 - Josefsson, Ida A1 - Rajkovic, Ivan A1 - Schreck, Simon A1 - Quevedo, Wilson A1 - Beye, Martin A1 - Grübel, 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 - Odelius, Michael A1 - Föhlisch, Alexander T1 - Anti-Stokes resonant x-ray Raman scattering for atom specific and excited state selective dynamics JF - NEW JOURNAL OF PHYSICS N2 - Ultrafast electronic and structural dynamics of matter govern rate and selectivity of chemical reactions, as well as phase transitions and efficient switching in functional materials. Since x-rays determine electronic and structural properties with elemental, chemical, orbital and magnetic selectivity, short pulse x-ray sources have become central enablers of ultrafast science. Despite of these strengths, ultrafast x-rays have been poor at picking up excited state moieties from the unexcited ones. With time-resolved anti-Stokes resonant x-ray Raman scattering (AS-RXRS) performed at the LCLS, and ab initio theory we establish background free excited state selectivity in addition to the elemental, chemical, orbital and magnetic selectivity of x-rays. This unparalleled selectivity extracts low concentration excited state species along the pathway of photo induced ligand exchange of Fe(CO)(5) in ethanol. Conceptually a full theoretical treatment of all accessible insights to excited state dynamics with AS-RXRS with transform-limited x-ray pulses is given-which will be covered experimentally by upcoming transform-limited x-ray sources. KW - ultrafast photochemistry KW - excited state selectivity KW - anti-Stokes resonant x-ray raman scattering KW - free electron lasers KW - resonant inelastic x-ray scattering Y1 - 2016 U6 - https://doi.org/10.1088/1367-2630/18/10/103011 SN - 1367-2630 VL - 18 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Kunnus, Kristjan A1 - Josefsson, I. A1 - Rajkovic, Ivan A1 - Schreck, Simon A1 - Quevedo, Wilson A1 - Beye, Martin A1 - Weniger, C. A1 - Gruebel, S. A1 - Scholz, M. A1 - Nordlund, D. A1 - Zhang, W. A1 - Hartsock, R. W. A1 - Gaffney, K. J. A1 - Schlotter, W. F. A1 - Turner, J. J. A1 - Kennedy, B. A1 - Hennies, F. A1 - de Groot, F. M. F. A1 - Techert, S. A1 - Odelius, Michael A1 - Wernet, Ph. A1 - Föhlisch, Alexander T1 - Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)(5) to Fe(CO)(4)EtOH JF - Structural dynamics N2 - We utilized femtosecond time-resolved resonant inelastic X-ray scattering and ab initio theory to study the transient electronic structure and the photoinduced molecular dynamics of a model metal carbonyl photocatalyst Fe(CO)(5) in ethanol solution. We propose mechanistic explanation for the parallel ultrafast intra-molecular spin crossover and ligation of the Fe(CO)(4) which are observed following a charge transfer photoexcitation of Fe(CO)(5) as reported in our previous study [ Wernet et al., Nature 520, 78 (2015)]. We find that branching of the reaction pathway likely happens in the (1)A(1) state of Fe(CO)(4). A sub-picosecond time constant of the spin crossover from B-1(2) to B-3(2) is rationalized by the proposed B-1(2) -> (1)A(1) -> B-3(2) mechanism. Ultrafast ligation of the B-1(2) Fe(CO)(4) state is significantly faster than the spin-forbidden and diffusion limited ligation process occurring from the B-3(2) Fe(CO)(4) ground state that has been observed in the previous studies. We propose that the ultrafast ligation occurs via B-1(2) -> (1)A(1) -> (1)A'Fe(CO)(4)EtOH pathway and the time scale of the (1)A(1) Fe(CO)(4) state ligation is governed by the solute-solvent collision frequency. Our study emphasizes the importance of understanding the interaction of molecular excited states with the surrounding environment to explain the relaxation pathways of photoexcited metal carbonyls in solution. (C) 2016 Author(s). Y1 - 2016 U6 - https://doi.org/10.1063/1.4941602 SN - 2329-7778 VL - 3 PB - American Institute of Physics CY - Washington ER - TY - JOUR A1 - Beye, Martin A1 - Öberg, Henrik A1 - Xin, Hongliang A1 - Dakovski, Georgi L. A1 - Föhlisch, Alexander A1 - Gladh, Jorgen A1 - Hantschmann, Markus A1 - Hieke, Florian A1 - Kaya, Sarp A1 - Kühn, Danilo A1 - LaRue, Jerry A1 - Mercurio, Giuseppe A1 - Minitti, Michael P. A1 - Mitra, Ankush A1 - Moeller, Stefan P. A1 - Ng, May Ling A1 - Nilsson, Anders A1 - Nordlund, Dennis A1 - Norskov, Jens A1 - Öström, Henrik A1 - Ogasawara, Hirohito A1 - Persson, Mats A1 - Schlotter, William F. A1 - Sellberg, Jonas A. A1 - Wolf, Martin A1 - Abild-Pedersen, Frank A1 - Pettersson, Lars G. M. A1 - Wurth, Wilfried T1 - Chemical Bond Activation Observed with an X-ray Laser JF - The journal of physical chemistry letters N2 - The concept of bonding and antibonding orbitals is fundamental in chemistry. The population of those orbitals and the energetic difference between the two reflect the strength of the bonding interaction. Weakening the bond is expected to reduce this energetic splitting, but the transient character of bond-activation has so far prohibited direct experimental access. Here we apply time-resolved soft X-ray spectroscopy at a free electron laser to directly observe the decreased bonding antibonding splitting following bond-activation using an ultrashort optical laser pulse. Y1 - 2016 U6 - https://doi.org/10.1021/acs.jpclett.6b01543 SN - 1948-7185 VL - 7 SP - 3647 EP - 3651 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Eckert, Sebastian A1 - Miedema, P. S. A1 - Quevedo, W. A1 - Fondell, Mattis A1 - Beye, Martin A1 - Pietzsch, Annette A1 - Ross, M. A1 - Khalil, M. A1 - Föhlisch, Alexander T1 - Molecular structures and protonation state of 2-Mercaptopyridine in aqueous solution JF - Chemical physics letters N2 - The speciation of 2-Mercaptopyridine in aqueous solution has been investigated with nitrogen 1s Near Edge X-ray Absorption Fine Structure spectroscopy and time dependent Density Functional Theory. The prevalence of distinct species as a function of the solvent basicity is established. No indications of dimerization towards high concentrations are found. The determination of different molecular structures of 2-Mercaptopyridine in aqueous solution is put into the context of proton-transfer in keto-enol and thione-thiol tautomerisms. (C) 2016 The Authors. Published by Elsevier B.V. Y1 - 2016 U6 - https://doi.org/10.1016/j.cplett.2016.01.050 SN - 0009-2614 SN - 1873-4448 VL - 647 SP - 103 EP - 106 PB - Elsevier CY - Amsterdam ER - TY - GEN A1 - Eckert, Sebastian A1 - Miedema, Piter A1 - Quevedo, Wilson A1 - O'Cinneide, B. A1 - Fondell, Mattis A1 - Beye, Martin A1 - Pietzsch, Annette A1 - Ross, Matthew R. A1 - Khalil, Munira A1 - Föhlisch, Alexander T1 - Molecular structures and protonation state of 2-Mercaptopyridine in aqueous solution T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - The speciation of 2-Mercaptopyridine in aqueous solution has been investigated with nitrogen 1s Near Edge X-ray Absorption Fine Structure spectroscopy and time dependent Density Functional Theory. The prevalence of distinct species as a function of the solvent basicity is established. No indications of dimerization towards high concentrations are found. The determination of different molecular structures of 2-Mercaptopyridine in aqueous solution is put into the context of proton-transfer in keto-enol and thione-thiol tautomerisms. (C) 2016 The Authors. Published by Elsevier B.V. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 953 KW - ray-emission-spectroscopy KW - x-ray KW - hydroxypyridine-pyridone KW - protomeric equilibria KW - self-association KW - CU(110) KW - valence Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-437473 SN - 1866-8372 IS - 953 SP - 103 EP - 106 ER -