TY - JOUR A1 - Rubensson, Jan-Erik A1 - Soderstrom, Johan A1 - Binggeli, Christian A1 - Grasjo, Joakim A1 - Andersson, Johan A1 - Sathe, Conny A1 - Hennies, Franz A1 - Bisogni, Valentina A1 - Huang, Yaobo A1 - Olalde, Paul A1 - Schmitt, Thorsten A1 - Strocov, Vladimir N. A1 - Föhlisch, Alexander A1 - Kennedy, Brian A1 - Pietzsch, Annette T1 - Rydberg-Resolved Resonant Inelastic Soft X-Ray Scattering: Dynamics at Core Ionization Thresholds JF - Physical review letters N2 - Resonant inelastic x-ray scattering spectra excited in the immediate vicinity of the core-level ionization thresholds of N-2 have been recorded. Final states of well-resolved symmetry-selected Rydberg series converging to valence-level ionization thresholds with vibrational excitations are observed. The results are well described by a quasi-two-step model which assumes that the excited electron is unaffected by the radiative decay. This threshold dynamics simplifies the interpretation of resonant inelastic x-ray scattering spectra considerably and facilitates characterization of low-energy excited final states in molecular systems. Y1 - 2015 U6 - https://doi.org/10.1103/PhysRevLett.114.133001 SN - 0031-9007 SN - 1079-7114 VL - 114 IS - 13 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Yin, Zhong A1 - Rajkovic, Ivan A1 - Kubicek, Katharina A1 - Quevedo, Wilson A1 - Pietzsch, Annette A1 - Wernet, Philippe A1 - Föhlisch, Alexander A1 - Techert, Simone T1 - Probing the Hofmeister effect with ultrafast core-hole spectroscopy JF - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry N2 - In the current work, X-ray emission spectra of aqueous solutions of different inorganic salts within the Hofmeister series are presented. The results reflect the direct interaction of the ions with the water molecules and therefore, reveal general properties of the salt-water interactions. Within the experimental precision a significant effect of the ions on the water structure has been observed but no ordering according to the structure maker/structure breaker concept could be mirrored in the results indicating that the Hofmeister effect if existent may be caused by more complex interactions. Y1 - 2014 U6 - https://doi.org/10.1021/jp504577a SN - 1520-6106 VL - 118 IS - 31 SP - 9398 EP - 9403 PB - American Chemical Society CY - Washington ER - TY - GEN A1 - Eschenlohr, Andrea A1 - Battiato, Mario A1 - Maldonado, P. A1 - Pontius, N. A1 - Kachel, T. A1 - Holldack, K. A1 - Mitzner, Rolf A1 - Föhlisch, Alexander A1 - Oppeneer, P. M. A1 - Stamm, Christian T1 - Optical excitation of thin magnetic layers in multilayer structures Reply T2 - Nature materials Y1 - 2014 U6 - https://doi.org/10.1038/nmat3851 SN - 1476-1122 SN - 1476-4660 VL - 13 IS - 2 SP - 102 EP - 103 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Yin, Zhong A1 - Inhester, Ludger A1 - Veedu, Sreevidya Thekku A1 - Quevedo, Wilson A1 - Pietzsch, Annette A1 - Wernet, Philippe A1 - Groenhof, Gerrit A1 - Föhlisch, Alexander A1 - Grubmueller, Helmut A1 - Techert, Simone T1 - Cationic and Anionic Impact on the Electronic Structure of Liquid Water JF - The journal of physical chemistry letters N2 - Hydration shells around ions are crucial for many fundamental biological and chemical processes. Their local physicochemical properties are quite different from those of bulk water and hard to probe experimentally. We address this problem by combining soft X-ray spectroscopy using a liquid jet and molecular dynamics (MD) simulations together with ab initio electronic structure calculations to elucidate the water ion interaction in a MgCl2 solution at the molecular level. Our results reveal that salt ions mainly affect the electronic properties of water molecules in close vicinity and that the oxygen K-edge X-ray emission spectrum of water molecules in the first solvation shell differs significantly from that of bulk water. Ion-specific effects are identified by fingerprint features in the water X-ray emission spectra. While Mg2+ ions cause a bathochromic shift of the water lone pair orbital, the 3p orbital of the Cl- ions causes an additional peak in the water emission spectrum at around 528 eV. Y1 - 2017 U6 - https://doi.org/10.1021/acs.jpclett.7b01392 SN - 1948-7185 VL - 8 SP - 3759 EP - 3764 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Schreck, Simon A1 - Pietzsch, Annette A1 - Kennedy, Brian A1 - Sathe, Conny A1 - Miedema, Piter S. A1 - Techert, Simone A1 - Strocov, Vladimir N. A1 - Schmitt, Thorsten A1 - Hennies, Franz A1 - Rubensson, Jan-Erik A1 - Föhlisch, Alexander T1 - Ground state potential energy surfaces around selected atoms from resonant inelastic x-ray scattering JF - Scientific reports N2 - Thermally driven chemistry as well as materials’ functionality are determined by the potential energy surface of a systems electronic ground state. This makes the potential energy surface a central and powerful concept in physics, chemistry and materials science. However, direct experimental access to the potential energy surface locally around atomic centers and to its long-range structure are lacking. Here we demonstrate how sub-natural linewidth resonant inelastic soft x-ray scattering at vibrational resolution is utilized to determine ground state potential energy surfaces locally and detect long-range changes of the potentials that are driven by local modifications. We show how the general concept is applicable not only to small isolated molecules such as O2 but also to strongly interacting systems such as the hydrogen bond network in liquid water. The weak perturbation to the potential energy surface through hydrogen bonding is observed as a trend towards softening of the ground state potential around the coordinating atom. The instrumental developments in high resolution resonant inelastic soft x-ray scattering are currently accelerating and will enable broad application of the presented approach. With this multidimensional potential energy surfaces that characterize collective phenomena such as (bio)molecular function or high-temperature superconductivity will become accessible in near future. Y1 - 2016 U6 - https://doi.org/10.1038/srep20054 SN - 2045-2322 VL - 6 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Thielemann-Kühn, Nele A1 - Schick, Daniel A1 - Pontius, Niko A1 - Trabant, Christoph A1 - Mitzner, Rolf A1 - Holldack, Karsten A1 - Zabel, Hartmut A1 - Föhlisch, Alexander A1 - Schuessler-Langeheine, Christian T1 - Ultrafast and Energy-Efficient Quenching of Spin Order: Antiferromagnetism Beats Ferromagnetism JF - Physical review letters N2 - By comparing femtosecond laser pulse induced ferro- and antiferromagnetic dynamics in one and the same material-metallic dysprosium-we show both to behave fundamentally different. Antiferromagnetic order is considerably faster and much more efficiently reduced by optical excitation than its ferromagnetic counterpart. We assign the fast and extremely efficient process in the antiferromagnet to an interatomic transfer of angular momentum within the spin system. Our findings imply that this angular momentum transfer channel is effective in other magnetic metals with nonparallel spin alignment. They also point out a possible route towards energy-efficient spin manipulation for magnetic devices. Y1 - 2017 U6 - https://doi.org/10.1103/PhysRevLett.119.197202 SN - 0031-9007 SN - 1079-7114 VL - 119 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Miedema, P. S. A1 - Mitzner, Rolf A1 - Ganschow, S. A1 - Föhlisch, Alexander A1 - Beye, Martin T1 - X-ray spectroscopy on the active ion in laser crystals JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - The active ions in typical laser crystals were studied with Resonant Inelastic X-ray Scattering (RIXS) and Partial Fluorescence Yield X-ray Absorption (PFY-XAS) spectroscopies as solid state model systems for dilute active centers. We analyzed Ti3+ and Cr3+ in alpha-Al2O3:Ti3+ and LiCaAlF6:Cr3+, respectively. The comparison of experimental data with semi-empirical multiplet calculations provides insights into the electronic structure and shows how measured crystal field energies are related across different spectroscopies. Y1 - 2017 U6 - https://doi.org/10.1039/c7cp03026f SN - 1463-9076 SN - 1463-9084 VL - 19 SP - 21800 EP - 21806 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Decker, Régis A1 - Born, Artur A1 - Büchner, Robby A1 - Ruotsalainen, Kari A1 - Stråhlman, Christian A1 - Neppl, Stefan A1 - Haverkamp, Robert A1 - Pietzsch, Annette A1 - Föhlisch, Alexander T1 - Measuring the atomic spin-flip scattering rate by x-ray emission spectroscopy JF - Scientific reports N2 - While extensive work has been dedicated to the measurement of the demagnetization time following an ultra-short laser pulse, experimental studies of its underlying microscopic mechanisms are still scarce. In transition metal ferromagnets, one of the main mechanism is the spin-flip of conduction electrons driven by electron-phonon scattering. Here, we present an original experimental method to monitor the electron-phonon mediated spin-flip scattering rate in nickel through the stringent atomic symmetry selection rules of x-ray emission spectroscopy. Increasing the phonon population leads to a waning of the 3d -> 2p(3/2) decay peak intensity, which reflects an increase of the angular momentum transfer scattering rate attributed to spin-flip. We find a spin relaxation time scale in the order of 50 fs in the 3d-band of nickel at room temperature, while consistantly, no such peak evolution is observed for the diamagnetic counterexample copper, using the same method. Y1 - 2019 U6 - https://doi.org/10.1038/s41598-019-45242-8 SN - 2045-2322 VL - 9 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Liu, Ji-Cai A1 - Vaz da Cruz, Vinicius A1 - Polyutov, Sergey A1 - Föhlisch, Alexander T1 - Recoil-induced dissociation in hard-x-ray photoionization JF - Physical review : A, Atomic, molecular, and optical physics N2 - We predict the recoil-induced molecular dissociation in hard-x-ray photoionization. The recoil effect is caused by electronic and photon momentum exchange with the molecule. We show the strong role of relativistic effects for the studied molecular fragmentation. The recoil-induced fragmentation of the molecule is caused by elongation of the bond due to the vibrational recoil effect and because of the centrifugal force caused by the rotational recoil. The calculations of the x-ray photoelectron spectra of the H-2 and NO molecules show that the predicted effects can be observed in high-energy synchrotrons like SOLEIL, SPring-8, PETRA, and XFEL SACLA. The relativistic effect enhances the recoil momentum transfer and makes it strongly sensitive to the direction of ejection of the fast photoelectron with respect to the photon momentum. Y1 - 2019 U6 - https://doi.org/10.1103/PhysRevA.100.053408 SN - 2469-9926 SN - 2469-9934 VL - 100 IS - 5 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Büchner, Robby A1 - Fondell, Mattis A1 - Mascarenhas, Eric Johnn A1 - Pietzsch, Annette A1 - Vaz da Cruz, Vinícius A1 - Föhlisch, Alexander T1 - How hydrogen bonding amplifies isomeric differences in pyridones toward strong changes in acidity and tautomerism JF - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry N2 - Steric hindrance of hydration and hydrogen bond enhancement by localized charges have been identified as key factors for the massive chemical differences between the hydroxypyridine/pyridone isomers in aqueous solution. While all isomers occur mainly in the hydroxypyridine form in the gas phase, they differ by more than 3 orders of magnitude both in their acidity and tautomeric equilibrium constants upon hydration. By monitoring the electronic and solvation structures as a function of the protonation state and the O- substitution position on the pyridine ring, the amplification of the isomeric differences in aqueous solution has been investigated. Near-edge X-ray absorption fine structure (NEXAFS) measurements at the N K-edge served as the probe of the chemical state. The combination of molecular dynamics simulations, complete active space self-consistent field (CASSCF), and time-dependent density functional theory (TD-DFT) spectral calculations contributes to unraveling the principles of tautomerism and acidity in multiple biochemical systems based on tautomerism. Y1 - 2021 U6 - https://doi.org/10.1021/acs.jpcb.0c10873 SN - 1520-6106 SN - 1520-5207 VL - 125 IS - 9 SP - 2372 EP - 2379 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Büchner, Robby A1 - Fondell, Mattis A1 - Haverkamp, Robert A1 - Pietzsch, Annette A1 - Vaz da Cruz, Vinícius A1 - Föhlisch, Alexander T1 - The porphyrin center as a regulator for metal-ligand covalency and pi hybridization in the entire molecule JF - Physical chemistry, chemical physics : PCCP ; a journal of European Chemical Societies N2 - The central moiety of porphyrins is shown to control the charge state of the inner complex and links it by covalent interaction to the peripheral substituents. This link, which enables the versatile functions of porphyrins, is not picked up in the established, reduced four orbital picture [Gouterman, J. Mol. Spectrosc., 1961, 6, 138]. X-ray absorption spectroscopy at the N K-edge with density functional theory approaches gives access to the full electronic structure, in particular the pi* manifold beyond the Gouterman orbitals. Systematic variation of the central moiety highlights two linked, governing trends: The ionicity of the porphyrin center increases from the aminic N-H to N-Cu to N-Zn to N-Mg to the iminic N:. At the same time covalency with peripheral substituents increases and compensates the buildup of high charge density at the coordinated nitrogen sites. Y1 - 2021 U6 - https://doi.org/10.1039/d1cp03944j SN - 1463-9076 SN - 1463-9084 VL - 23 IS - 43 SP - 24765 EP - 24772 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Eckert, Sebastian A1 - Vaz da Cruz, Vinícius A1 - Ochmann, Miguel A1 - Ahnen, Inga von A1 - Föhlisch, Alexander A1 - Huse, Nils T1 - Breaking the symmetry of pyrimidine BT - solvent effects and core-excited state dynamics JF - The journal of physical chemistry letters N2 - Symmetry and its breaking crucially define the chemical properties of molecules and their functionality. Resonant inelastic X-ray scattering is a local electronic structure probe reporting on molecular symmetry and its dynamical breaking within the femtosecond scattering duration. Here, we study pyrimidine, a system from the C-2v point group, in an aqueous solution environment, using scattering though its 2a(2) resonance. Despite the absence of clean parity selection rules for decay transitions from in-plane orbitals, scattering channels including decay from the 7b(2) and 11a(1) orbitals with nitrogen lone pair character are a direct probe for molecular symmetry. Computed spectra of explicitly solvated molecules sampled from a molecular dynamics simulation are combined with the results of a quantum dynamical description of the X-ray scattering process. We observe dominant signatures of core-excited Jahn-Teller induced symmetry breaking for resonant excitation. Solvent contributions are separable by shortening of the effective scattering duration through excitation energy detuning. Y1 - 2021 U6 - https://doi.org/10.1021/acs.jpclett.1c01865 SN - 1948-7185 VL - 12 IS - 35 SP - 8637 EP - 8643 PB - American Chemical Society CY - Washington 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 - Kunnus, Kristjan A1 - Rajkovic, Ivan A1 - Schreck, Simon A1 - Quevedo, Wilson A1 - Eckert, Sebastian A1 - Beye, Martin A1 - Suljoti, Edlira A1 - Weniger, Christian A1 - Kalus, Christian A1 - Gruebel, 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 - Föhlisch, Alexander T1 - A setup for resonant inelastic soft x-ray scattering on liquids at free electron laser light sources JF - Review of scientific instruments : a monthly journal devoted to scientific instruments, apparatus, and techniques N2 - We present a flexible and compact experimental setup that combines an in vacuum liquid jet with an x-ray emission spectrometer to enable static and femtosecond time-resolved resonant inelastic soft x-ray scattering (RIXS) measurements from liquids at free electron laser (FEL) light sources. We demonstrate the feasibility of this type of experiments with the measurements performed at the Linac Coherent Light Source FEL facility. At the FEL we observed changes in the RIXS spectra at high peak fluences which currently sets a limit to maximum attainable count rate at FELs. The setup presented here opens up new possibilities to study the structure and dynamics in liquids. Y1 - 2012 U6 - https://doi.org/10.1063/1.4772685 SN - 0034-6748 VL - 83 IS - 12 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Eckert, Sebastian A1 - Norell, Jesper A1 - Miedema, Piter S. A1 - Beye, Martin A1 - Fondell, Mattis A1 - Quevedo, Wilson A1 - Kennedy, Brian A1 - Hantschmann, Markus A1 - Pietzsch, Annette A1 - van Kuiken, Benjamin A1 - Ross, Matthew A1 - Minitti, Michael P. A1 - Moeller, Stefan P. A1 - Schlotter, William F. A1 - Khalil, Munira A1 - Odelius, Michael A1 - Föhlisch, Alexander T1 - Untersuchung unabhängiger N‐H‐ und N‐C‐Bindungsverformungen auf ultrakurzen Zeitskalen mit resonanter inelastischer Röntgenstreuung JF - Angewandte Chemie N2 - Die Femtosekundendynamik nach resonanten Photoanregungen mit optischen und Röntgenpulsen ermöglicht eine selektive Verformung von chemischen N‐H‐ und N‐C‐Bindungen in 2‐Thiopyridon in wässriger Lösung. Die Untersuchung der orbitalspezifischen elektronischen Struktur und ihrer Dynamik auf ultrakurzen Zeitskalen mit resonanter inelastischer Röntgenstreuung an der N1s‐Resonanz am Synchrotron und dem Freie‐Elektronen‐Laser LCLS in Kombination mit quantenchemischen Multikonfigurationsberechnungen erbringen den direkten Nachweis dieser kontrollierten photoinduzierten Molekülverformungen und ihrer ultrakurzen Zeitskala. KW - Photochemie KW - Protonierung KW - RIXS (resonante inelastische Röntgenstreuung) KW - Selektiver Bindungsbruch KW - Stickstoff Y1 - 2017 U6 - https://doi.org/10.1002/ange.201700239 SN - 1521-3757 SN - 1521-3773 VL - 129 IS - 22 SP - 6184 EP - 6188 ER - TY - JOUR A1 - Eckert, Sebastian A1 - Norell, Jesper A1 - Miedema, Piter S. A1 - Beye, Martin A1 - Fondell, Mattis A1 - Quevedo, Wilson A1 - Kennedy, Brian A1 - Hantschmann, Markus A1 - Pietzsch, Annette A1 - Van Kuiken, Benjamin E. A1 - Ross, Matthew A1 - Minitti, Michael P. A1 - Moeller, Stefan P. A1 - Schlotter, William F. A1 - Khalil, Munira A1 - Odelius, Michael A1 - Föhlisch, Alexander T1 - Ultrafast Independent N-H and N-C Bond Deformation Investigated with Resonant Inelastic X-Ray Scattering JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition N2 - The femtosecond excited-state dynamics following resonant photoexcitation enable the selective deformation of N-H and N-C chemical bonds in 2-thiopyridone in aqueous solution with optical or X-ray pulses. In combination with multiconfigurational quantum-chemical calculations, the orbital-specific electronic structure and its ultrafast dynamics accessed with resonant inelastic X-ray scattering at the N 1s level using synchrotron radiation and the soft X-ray free-electron laser LCLS provide direct evidence for this controlled photoinduced molecular deformation and its ultrashort time-scale. KW - nitrogen KW - photochemistry KW - protonation KW - RIXS (resonant inelastic X-ray scattering) KW - selective bond cleavage Y1 - 2017 U6 - https://doi.org/10.1002/anie.201700239 SN - 1433-7851 SN - 1521-3773 VL - 56 SP - 6088 EP - 6092 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Vaz da Cruz, Vinicius A1 - Ertan, Emelie A1 - Couto, Rafael C. A1 - Eckert, Sebastian A1 - Fondell, Mattis A1 - Dantz, Marcus A1 - Kennedy, Brian A1 - Schmitt, Thorsten A1 - Pietzsch, Annette A1 - Guimaraes, Freddy F. A1 - Ågren, Hans A1 - Odelius, Michael A1 - Föhlisch, Alexander A1 - Kimberg, Victor T1 - A study of the water molecule using frequency control over nuclear dynamics in resonant X-ray scattering JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - In this combined theoretical and experimental study we report a full analysis of the resonant inelastic X-ray scattering (RIXS) spectra of H2O, D2O and HDO. We demonstrate that electronically-elastic RIXS has an inherent capability to map the potential energy surface and to perform vibrational analysis of the electronic ground state in multimode systems. We show that the control and selection of vibrational excitation can be performed by tuning the X-ray frequency across core-excited molecular bands and that this is clearly reflected in the RIXS spectra. Using high level ab initio electronic structure and quantum nuclear wave packet calculations together with high resolution RIXS measurements, we discuss in detail the mode coupling, mode localization and anharmonicity in the studied systems. Y1 - 2017 U6 - https://doi.org/10.1039/c7cp01215b SN - 1463-9076 SN - 1463-9084 VL - 19 SP - 19573 EP - 19589 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Norell, Jesper A1 - Eckert, Sebastian A1 - Van Kuiken, Benjamin E. A1 - Föhlisch, Alexander A1 - Odelius, Michael T1 - Ab initio simulations of complementary K-edges and solvatization effects for detection of proton transfer in aqueous 2-thiopyridone JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr N2 - The nitrogen and sulfur K-edge X-ray absorption spectra of aqueous 2-thiopyridone, a model system for excited-state proton transfer in several recent time-resolved measurements, have been simulated from ab initio molecular dynamics. Spectral signatures of the local intra- and inter-molecular structure are identified and rationalized, which facilitates experimental interpretation and optimization. In particular, comparison of aqueous and gas phase spectrum simulations assesses the previously unquantified solvatization effects, where hydrogen bonding is found to yield solvatochromatic shifts up to nearly 1 eV of the main peak positions. Thereby, while each K-edge can still decisively determine the local protonation of its core-excited site, only their combined, complementary fingerprints allow separating all of the three relevant molecular forms, giving a complete picture of the proton transfer. Y1 - 2019 U6 - https://doi.org/10.1063/1.5109840 SN - 0021-9606 SN - 1089-7690 VL - 151 IS - 11 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Eckert, Sebastian A1 - Niskanen, Johannes A1 - Jay, Raphael Martin A1 - Miedema, Piter S. A1 - Fondell, Mattis A1 - Kennedy, Brian A1 - Quevedo, Wilson A1 - Iannuzzi, Marcella A1 - Föhlisch, Alexander T1 - Valence orbitals and local bond dynamics around N atoms of histidine under X-ray irradiation JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - The valence orbitals of aqueous histidine under basic, neutral and acidic conditions and their X-ray induced transformations have been monitored through N 1s resonant inelastic X-ray scattering. Using density functional ab initio molecular dynamics simulations in the core-hole state within the Z + 1 approximation, core-excitation-induced molecular transformations are quantified. Spectroscopic evidence for a highly directional X-ray-induced local N-H dissociation within the scattering duration is presented for acidic histidine. Our report demonstrates a protonation-state and chemical-environment dependent propensity for a molecular dissociation, which is induced by the absorption of high energy photons. This case study indicates that structural deformations in biomolecules under exposure to ionizing radiation, yielding possible alteration or loss of function, is highly dependent on the physiological state of the molecule upon irradiation. Y1 - 2017 U6 - https://doi.org/10.1039/c7cp05713j SN - 1463-9076 SN - 1463-9084 VL - 19 SP - 32091 EP - 32098 PB - Royal Society of Chemistry CY - Cambridge 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 -