@article{YinRajkovicVeeduetal.2015, author = {Yin, Zhong and Rajkovic, Ivan and Veedu, Sreevidya Thekku and Deinert, Sascha and Raiser, Dirk and Jain, Rohit and Fukuzawa, Hironobu and Wada, Shin-ichi and Quevedo, Wilson and Kennedy, Brian and Schreck, Simon and Pietzsch, Annette and Wernet, Philippe and Ueda, Kyoshi and F{\"o}hlisch, Alexander and Techert, Simone}, title = {Ionic solutions probed by resonant inelastic X-ray scattering}, series = {Zeitschrift f{\"u}r physikalische Chemie : international journal of research in physical chemistry and chemical physics}, volume = {229}, journal = {Zeitschrift f{\"u}r physikalische Chemie : international journal of research in physical chemistry and chemical physics}, number = {10-12}, publisher = {De Gruyter}, address = {Berlin}, issn = {0942-9352}, doi = {10.1515/zpch-2015-0610}, pages = {1855 -- 1867}, year = {2015}, abstract = {X-ray spectroscopy is a powerful tool to study the local charge distribution of chemical systems. Together with the liquid jet it becomes possible to probe chemical systems in their natural environment, the liquid phase. In this work, we present X-ray absorption (XA), X-ray emission (XE) and resonant inelastic X-ray scattering (RIXS) data of pure water and various salt solutions and show the possibilities these methods offer to elucidate the nature of ion-water interaction.}, language = {en} } @article{YinRajkovicKubiceketal.2014, author = {Yin, Zhong and Rajkovic, Ivan and Kubicek, Katharina and Quevedo, Wilson and Pietzsch, Annette and Wernet, Philippe and F{\"o}hlisch, Alexander and Techert, Simone}, title = {Probing the Hofmeister effect with ultrafast core-hole spectroscopy}, series = {The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces \& biophysical chemistry}, volume = {118}, journal = {The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces \& biophysical chemistry}, number = {31}, publisher = {American Chemical Society}, address = {Washington}, issn = {1520-6106}, doi = {10.1021/jp504577a}, pages = {9398 -- 9403}, year = {2014}, abstract = {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.}, language = {en} } @article{YinInhesterVeeduetal.2017, author = {Yin, Zhong and Inhester, Ludger and Veedu, Sreevidya Thekku and Quevedo, Wilson and Pietzsch, Annette and Wernet, Philippe and Groenhof, Gerrit and F{\"o}hlisch, Alexander and Grubmueller, Helmut and Techert, Simone}, title = {Cationic and Anionic Impact on the Electronic Structure of Liquid Water}, series = {The journal of physical chemistry letters}, volume = {8}, journal = {The journal of physical chemistry letters}, publisher = {American Chemical Society}, address = {Washington}, issn = {1948-7185}, doi = {10.1021/acs.jpclett.7b01392}, pages = {3759 -- 3764}, year = {2017}, abstract = {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.}, language = {en} } @article{XinLaRueObergetal.2015, author = {Xin, Hong and LaRue, Jerry and Oberg, Henrik and Beye, Martin and Turner, J. J. and Gladh, J{\"o}rgen and Ng, May L. and Sellberg, Jonas A. and Kaya, Sarp and Mercurio, G. and Hieke, F. and Nordlund, Dennis and Schlotter, William F. and Dakovski, Georgi L. and Minitti, Michael P. and F{\"o}hlisch, Alexander and Wolf, Martin and Wurth, Wilfried and Ogasawara, Hirohito and Norskov, Jens K. and Ostrom, Henrik and Pettersson, Lars G. M. and Nilsson, Anders and Abild-Pedersen, Frank}, title = {Strong Influence of Coadsorbate Interaction on CO Desorption Dynamics on Ru(0001) Probed by Ultrafast X-Ray Spectroscopy and Ab Initio Simulations}, series = {Physical review letters}, volume = {114}, journal = {Physical review letters}, number = {15}, publisher = {American Physical Society}, address = {College Park}, issn = {0031-9007}, doi = {10.1103/PhysRevLett.114.156101}, pages = {6}, year = {2015}, abstract = {We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species. This is supported with the potential of mean force along the CO desorption path obtained from density-functional theory calculations. Charge density distribution and frozen-orbital analysis suggest that the oxygen-induced reduction of the Pauli repulsion, and consequent increase of the dative interaction between the CO 5 sigma and the charged Ru atom, is the electronic origin of the distinct desorption dynamics. Ab initio molecular dynamics simulations of CO desorption from Ru(0001) and oxygen-coadsorbed Ru(0001) provide further insights into the surface bond-breaking process.}, language = {en} } @article{WernetLeitnerJosefssonetal.2017, author = {Wernet, Philippe and Leitner, T. and Josefsson, Ida and Mazza, T. and Miedema, P. S. and Schroder, H. and Beye, Martin and Kunnus, K. and Schreck, S. and Radcliffe, P. and Dusterer, S. and Meyer, M. and Odelius, Michael and Fohlisch, Alexander}, title = {Communication: Direct evidence for sequential dissociation of gas-phase Fe(CO)(5) via a singlet pathway upon excitation at 266 nm}, series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, volume = {146}, journal = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-9606}, doi = {10.1063/1.4984774}, pages = {5}, year = {2017}, abstract = {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.}, language = {en} } @article{WernetKunnusSchrecketal.2012, author = {Wernet, Philippe and Kunnus, Kristjan and Schreck, Simon and Quevedo, Wilson and Kurian, Reshmi and Techert, Simone and de Groot, Frank M. F. and Odelius, Michael and F{\"o}hlisch, Alexander}, title = {Dissecting local atomic and intermolecular interactions of transition-metal ions in solution with selective X-ray spectroscopy}, series = {The journal of physical chemistry letters}, volume = {3}, journal = {The journal of physical chemistry letters}, number = {23}, publisher = {American Chemical Society}, address = {Washington}, issn = {1948-7185}, doi = {10.1021/jz301486u}, pages = {3448 -- 3453}, year = {2012}, abstract = {Determining covalent and charge-transfer contributions to bonding in solution has remained an experimental challenge. Here, the quenching of fluorescence decay channels as expressed in dips in the L-edge X-ray spectra of solvated 3d transition-metal ions and complexes was reported as a probe. With a full set of experimental and theoretical ab initio L-edge X-ray spectra of aqueous Cr3+, including resonant inelastic X-ray scattering, we address covalency and charge transfer for this prototypical transition-metal ion in solution. We dissect local atomic effects from intermolecular interactions and quantify X-ray optical effects. We find no evidence for the asserted ultrafast charge transfer to the solvent and show that the dips are readily explained by X-ray optical effects and local atomic state dependence of the fluorescence yield. Instead, we find, besides ionic interactions, a covalent contribution to the bonding in the aqueous complex of ligand-to-metal charge-transfer character.}, language = {en} } @article{WernetKunnusJosefssonetal.2015, author = {Wernet, Philippe and Kunnus, Kristjan and Josefsson, Ida and Rajkovic, Ivan and Quevedo, Wilson and Beye, Martin and Schreck, Simon and Gruebel, S. and Scholz, Mirko and Nordlund, Dennis and Zhang, Wenkai and Hartsock, Robert W. and Schlotter, William F. and Turner, Joshua J. and Kennedy, Brian and Hennies, Franz and de Groot, Frank M. F. and Gaffney, Kelly J. and Techert, Simone and Odelius, Michael and F{\"o}hlisch, Alexander}, title = {Orbital-specific mapping of the ligand exchange dynamics of Fe(CO)(5) in solution}, series = {Nature : the international weekly journal of science}, volume = {520}, journal = {Nature : the international weekly journal of science}, number = {7545}, publisher = {Nature Publ. Group}, address = {London}, issn = {0028-0836}, doi = {10.1038/nature14296}, pages = {78 -- 81}, year = {2015}, abstract = {Transition-metal complexes have long attracted interest for fundamental chemical reactivity studies and possible use in solar energy conversion(1,2). Electronic excitation, ligand loss from the metal centre, or a combination of both, creates changes in charge and spin density at the metal site(3-11) that need to be controlled to optimize complexes for photocatalytic hydrogen production(8) and selective carbon-hydrogen bond activation(9-11). An understanding at the molecular level of how transition-metal complexes catalyse reactions, and in particular of the role of the short-lived and reactive intermediate states involved, will be critical for such optimization. However, suitable methods for detailed characterization of electronic excited states have been lacking. Here we show, with the use of X-ray laser-based femtosecond-resolution spectroscopy and advanced quantum chemical theory to probe the reaction dynamics of the benchmark transition-metal complex Fe(CO)(5) in solution, that the photo-induced removal of CO generates the 16-electron Fe(CO)(4) species, a homogeneous catalyst(12,13) with an electron deficiency at the Fe centre(14,15), in a hitherto unreported excited singlet state that either converts to the triplet ground state or combines with a CO or solvent molecule to regenerate a penta-coordinated Fe species on a sub-picosecond timescale. This finding, which resolves the debate about the relative importance of different spin channels in the photochemistry of Fe(CO)(5) (refs 4, 16-20), was made possible by the ability of femtosecond X-ray spectroscopy to probe frontier-orbital interactions with atom specificity. We expect the method to be broadly applicable in the chemical sciences, and to complement approaches that probe structural dynamics in ultrafast processes.}, language = {en} } @article{VazdaCruzIgnatovaCoutoetal.2019, author = {Vaz da Cruz, Vin{\´i}cius and Ignatova, Nina and Couto, Rafael and Fedotov, Daniil and Rehn, Dirk R. and Savchenko, Viktoriia and Norman, Patrick and {\AA}gren, Hans and Polyutov, Sergey and Niskanen, Johannes and Eckert, Sebastian Oliver and Jay, Raphael Martin and Fondell, Mattis and Schmitt, Thorsten and Pietzsch, Annette and F{\"o}hlisch, Alexander and Odelius, Michael and Kimberg, Victor and Gel'mukhanov, Faris}, title = {Nuclear dynamics in resonant inelastic X-ray scattering and X-ray absorption of methanol}, series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, volume = {150}, journal = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, number = {23}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-9606}, doi = {10.1063/1.5092174}, pages = {20}, year = {2019}, abstract = {We report on a combined theoretical and experimental study of core-excitation spectra of gas and liquid phase methanol as obtained with the use of X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS). The electronic transitions are studied with computational methods that include strict and extended second-order algebraic diagrammatic construction [ADC(2) and ADC(2)-x], restricted active space second-order perturbation theory, and time-dependent density functional theory-providing a complete assignment of the near oxygen K-edge XAS. We show that multimode nuclear dynamics is of crucial importance for explaining the available experimental XAS and RIXS spectra. The multimode nuclear motion was considered in a recently developed "mixed representation" where dissociative states and highly excited vibrational modes are accurately treated with a time-dependent wave packet technique, while the remaining active vibrational modes are described using Franck-Condon amplitudes. Particular attention is paid to the polarization dependence of RIXS and the effects of the isotopic substitution on the RIXS profile in the case of dissociative core-excited states. Our approach predicts the splitting of the 2a RIXS peak to be due to an interplay between molecular and pseudo-atomic features arising in the course of transitions between dissociative core- and valence-excited states. The dynamical nature of the splitting of the 2a peak in RIXS of liquid methanol near pre-edge core excitation is shown. The theoretical results are in good agreement with our liquid phase measurements and gas phase experimental data available from the literature. (C) 2019 Author(s).}, language = {en} } @article{VazdaCruzEckertFoehlisch2021, author = {Vaz da Cruz, Vin{\´i}cius and Eckert, Sebastian Oliver and F{\"o}hlisch, Alexander}, title = {TD-DFT simulations of K-edge resonant inelastic X-ray scattering within the restricted subspace approximation}, series = {Physical chemistry, chemical physics : PCCP ; a journal of European Chemical Societies}, volume = {23}, journal = {Physical chemistry, chemical physics : PCCP ; a journal of European Chemical Societies}, number = {3}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/d0cp04726k}, pages = {1835 -- 1848}, year = {2021}, abstract = {A scheme for simulations of resonant inelastic X-ray scattering (RIXS) cross-sections within time-dependent density functional theory (TD-DFT) applying the restricted subspace approximation (RSA) is presented. Therein both occupied core and valence Kohn-Sham orbitals are included in the donor-space, while the accepting virtual orbital space in the linear response TD-DFT equations is restricted to efficiently compute both the valence- and core-excited states of the many electron system. This yields a consistent description of all states contributing to the RIXS scattering process within a single calculation. The introduced orbital truncation allows to automatize the method and facilitates RIXS simulations for systems considerably larger than ones accessible with wave-function based methods. Using the nitrogen K-edge RIXS spectra of 2-thiopyridone and its deprotonated anion as a showcase, the method is benchmarked for different exchange-correlation functionals, the impact of the RSA is evaluated, and the effects of explicit solvation are discussed. Improvements compared to simulations in the frozen orbital approximation are also assessed. The general applicability of the framework is further tested by comparison to experimental data from the literature. The use of TD-DFT core-excited states to the calculation of vibrationally resolved RIXS spectra is also investigated by combining potential energy scans along relevant coordinates with wave packet simulations.}, language = {en} } @misc{VazdaCruzErtanCoutoetal.2017, author = {Vaz da Cruz, Vinicius and Ertan, Emelie and Couto, Rafael C. and Eckert, Sebastian Oliver and Fondell, Mattis and Dantz, Marcus and Kennedy, Brian and Schmitt, Thorsten and Pietzsch, Annette and Guimar{\~a}es, Freddy F. and {\AA}gren, Hans and Gel'mukhanov, Faris and Odelius, Michael and F{\"o}hlisch, Alexander and Kimberg, Victor}, title = {A study of the water molecule using frequency control over nuclear dynamics in resonant X-ray scattering}, series = {Postprints der Universit{\"a}t Potsdam Mathematisch-Naturwissenschaftliche Reihe}, journal = {Postprints der Universit{\"a}t Potsdam Mathematisch-Naturwissenschaftliche Reihe}, number = {781}, issn = {1866-8372}, doi = {10.25932/publishup-43690}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-436901}, pages = {19573 -- 19589}, year = {2017}, abstract = {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.}, language = {en} } @article{VazdaCruzErtanCoutoetal.2017, author = {Vaz da Cruz, Vinicius and Ertan, Emelie and Couto, Rafael C. and Eckert, Sebastian Oliver and Fondell, Mattis and Dantz, Marcus and Kennedy, Brian and Schmitt, Thorsten and Pietzsch, Annette and Guimaraes, Freddy F. and {\AA}gren, Hans and Odelius, Michael and F{\"o}hlisch, Alexander and Kimberg, Victor}, title = {A study of the water molecule using frequency control over nuclear dynamics in resonant X-ray scattering}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {19}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/c7cp01215b}, pages = {19573 -- 19589}, year = {2017}, abstract = {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.}, language = {en} } @article{VazdaCruzEckertIannuzzietal.2019, author = {Vaz da Cruz, Vinicius and Eckert, Sebastian Oliver and Iannuzzi, Marcella and Ertan, Emelie and Pietzsch, Annette and Couto, Rafael C. and Niskanen, Johannes and Fondell, Mattis and Dantz, Marcus and Schmitt, Thorsten and Lu, Xingye and McNally, Daniel and Jay, Raphael Martin and Kimberg, Victor and F{\"o}hlisch, Alexander and Odelius, Michael}, title = {Probing hydrogen bond strength in liquid water by resonant inelastic X-ray scattering}, series = {Nature Communications}, volume = {10}, journal = {Nature Communications}, publisher = {Nature Publ. Group}, address = {London}, issn = {2041-1723}, doi = {10.1038/s41467-019-08979-4}, pages = {9}, year = {2019}, abstract = {Local probes of the electronic ground state are essential for understanding hydrogen bonding in aqueous environments. When tuned to the dissociative core-excited state at the O1s pre-edge of water, resonant inelastic X-ray scattering back to the electronic ground state exhibits a long vibrational progression due to ultrafast nuclear dynamics. We show how the coherent evolution of the OH bonds around the core-excited oxygen provides access to high vibrational levels in liquid water. The OH bonds stretch into the long-range part of the potential energy curve, which makes the X-ray probe more sensitive than infra-red spectroscopy to the local environment. We exploit this property to effectively probe hydrogen bond strength via the distribution of intramolecular OH potentials derived from measurements. In contrast, the dynamical splitting in the spectral feature of the lowest valence-excited state arises from the short-range part of the OH potential curve and is rather insensitive to hydrogen bonding.}, language = {en} } @article{VazdaCruzBuechnerFondelletal.2022, author = {Vaz da Cruz, Vinicius and B{\"u}chner, Robby and Fondell, Mattis and Pietzsch, Annette and Eckert, Sebastian Oliver and F{\"o}hlisch, Alexander}, title = {Targeting individual tautomers in equilibrium by resonant inelastic X-ray scattering}, series = {The journal of physical chemistry letters}, volume = {13}, journal = {The journal of physical chemistry letters}, number = {10}, publisher = {American Chemical Society}, address = {Washington}, issn = {1948-7185}, doi = {10.1021/acs.jpclett.1c03453}, pages = {2459 -- 2466}, year = {2022}, abstract = {Tautomerism is one of the most important forms of isomerism, owing to the facile interconversion between species and the large differences in chemical properties introduced by the proton transfer connecting the tautomers. Spectroscopic techniques are often used for the characterization of tautomers. In this context, separating the overlapping spectral response of coexisting tautomers is a long-standing challenge in chemistry. Here, we demonstrate that by using resonant inelastic X-ray scattering tuned to the core excited states at the site of proton exchange between tautomers one is able to experimentally disentangle the manifold of valence excited states of each tautomer in a mixture. The technique is applied to the prototypical keto-enol equilibrium of 3-hydroxypyridine in aqueous solution. We detect transitions from the occupied orbitals into the LUMO for each tautomer in solution, which report on intrinsic and hydrogen-bond-induced orbital polarization within the pi and sigma manifolds at the proton-transfer site.}, language = {en} } @article{ThielemannKuehnSchickPontiusetal.2017, author = {Thielemann-K{\"u}hn, Nele and Schick, Daniel and Pontius, Niko and Trabant, Christoph and Mitzner, Rolf and Holldack, Karsten and Zabel, Hartmut and F{\"o}hlisch, Alexander and Schuessler-Langeheine, Christian}, title = {Ultrafast and Energy-Efficient Quenching of Spin Order: Antiferromagnetism Beats Ferromagnetism}, series = {Physical review letters}, volume = {119}, journal = {Physical review letters}, publisher = {American Physical Society}, address = {College Park}, issn = {0031-9007}, doi = {10.1103/PhysRevLett.119.197202}, pages = {6}, year = {2017}, abstract = {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.}, language = {en} } @article{ThielemannKuehnHoffmannFoehlisch2012, author = {Thielemann-K{\"u}hn, Nele and Hoffmann, P. and F{\"o}hlisch, Alexander}, title = {A versatile detector for total fluorescence and electron yield experiments}, series = {Review of scientific instruments : a monthly journal devoted to scientific instruments, apparatus, and techniques}, volume = {83}, journal = {Review of scientific instruments : a monthly journal devoted to scientific instruments, apparatus, and techniques}, number = {9}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0034-6748}, doi = {10.1063/1.4754126}, pages = {3}, year = {2012}, abstract = {The combination of a non-coated silicon photodiode with electron repelling meshes makes a versatile detector for total fluorescence yield and electron yield techniques highly suitable for x-ray absorption spectroscopy. In particular, a copper mesh with a bias voltage allows to suppress or transmit the electron yield signal. The performance of this detection scheme has been characterized by near edge x-ray absorption fine structure studies of thermal oxidized silicon and sapphire. The results show that the new detector probes both electron yield and for a bias voltage exceeding the maximum photon energy the total fluorescence yield.}, language = {en} } @article{SunMiaoPietzschetal.2013, author = {Sun, Y. -P. and Miao, Q. and Pietzsch, Annette and Hennies, F. and Schmitt, T. and Strocov, V. N. and Andersson, Joakim and Kennedy, B. and Schlappa, J. and F{\"o}hlisch, Alexander and Gel\&rsquo, and mukhanov, F. and Rubensson, J. -E.}, title = {Interference between Resonant and Nonresonant Inelastic X-Ray Scattering}, series = {PHYSICAL REVIEW LETTERS}, volume = {110}, journal = {PHYSICAL REVIEW LETTERS}, number = {22}, publisher = {AMER PHYSICAL SOC}, address = {COLLEGE PK}, issn = {0031-9007}, doi = {10.1103/PhysRevLett.110.223001}, pages = {4}, year = {2013}, abstract = {A detailed study of inelastic x-ray scattering from the ground state to the (3)Sigma(g)(3 sigma(-1)(g)3s(g)(1)) state of the O-2 molecule is presented. The observed angular anisotropy shows that the vibrational excitations within this final state are strongly dependent on the polarization of the incident radiation. The analysis demonstrates that this is a manifestation of interference between resonant and direct nonresonant inelastic x-ray scattering. This interference provides a new tool to monitor nuclear dynamics by relative rotation of the polarization vectors of the incident and scattered photons.}, language = {en} } @article{SunHenniesPietzschetal.2011, author = {Sun, Y. -P. and Hennies, Franz and Pietzsch, Annette and Kennedy, B. and Schmitt, Thorsten and Strocov, Vladimir N. and Andersson, Joakim and Berglund, Martin and Rubensson, Jan-Erik and Aidas, K. and Gel'mukhanov, F. and Odelius, Michael and F{\"o}hlisch, Alexander}, title = {Intramolecular soft modes and intermolecular interactions in liquid acetone}, series = {Physical review : B, Condensed matter and materials physics}, volume = {84}, journal = {Physical review : B, Condensed matter and materials physics}, number = {13}, publisher = {American Physical Society}, address = {College Park}, issn = {1098-0121}, doi = {10.1103/PhysRevB.84.132202}, pages = {4}, year = {2011}, abstract = {Resonant inelastic x-ray scattering spectra excited at the O1s(-1)pi* resonance of liquid acetone are presented. Scattering to the electronic ground state shows a resolved vibrational progression where the dominant contribution is due to the C-O stretching mode, thus demonstrating a unique sensitivity of the method to the local potential energy surface in complex molecular systems. For scattering to electronically excited states, soft vibrational modes and, to a smaller extent, intermolecular interactions give a broadening, which blurs the vibrational fine structure. It is predicted that environmental broadening is dominant in aqueous acetone.}, language = {en} } @article{SunPietzschHenniesetal.2011, author = {Sun, Y-P and Pietzsch, Annette and Hennies, Franz and Rinkevicius, Z. and Karlsson, Hans O. and Schmitt, Thorsten and Strocov, Vladimir N. and Andersson, Joakim and Kennedy, B. and Schlappa, J. and F{\"o}hlisch, Alexander and Gel'mukhanov, F. and Rubensson, Jan-Erik}, title = {Internal symmetry and selection rules in resonant inelastic soft x-ray scattering}, series = {Journal of physics : B, Atomic, molecular and optical physics}, volume = {44}, journal = {Journal of physics : B, Atomic, molecular and optical physics}, number = {16}, publisher = {IOP Publ. Ltd.}, address = {Bristol}, issn = {0953-4075}, doi = {10.1088/0953-4075/44/16/161002}, pages = {5}, year = {2011}, abstract = {Resonant inelastic soft x-ray scattering spectra excited at the dissociative 1 sigma(g) -> 3 sigma(u) resonance in gas-phase O(2) are presented and discussed in terms of state-of-the-art molecular theory. A new selection rule due to internal spin coupling is established, facilitating a deep analysis of the valence excited final states. Furthermore, it is found that a commonly accepted symmetry selection rule due to orbital parity breaks down, as the core hole and excited electron swap parity, thereby opening the symmetry forbidden 3 sigma(g) decay channel.}, language = {en} } @article{SellbergMcQueenLaksmonoetal.2015, author = {Sellberg, Jonas A. and McQueen, Trevor A. and Laksmono, Hartawan and Schreck, Simon and Beye, Martin and DePonte, Daniel P. and Kennedy, Brian and Nordlund, Dennis and Sierra, Raymond G. and Schlesinger, Daniel and Tokushima, Takashi and Zhovtobriukh, Iurii and Eckert, Sebastian Oliver and Segtnan, Vegard H. and Ogasawara, Hirohito and Kubicek, Katharina and Techert, Simone and Bergmann, Uwe and Dakovski, Georgi L. and Schlotter, William F. and Harada, Yoshihisa and Bogan, Michael J. and Wernet, Philippe and F{\"o}hlisch, Alexander and Pettersson, Lars G. M. and Nilsson, Anders}, title = {X-ray emission spectroscopy of bulk liquid water in "no-man's land"}, series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, volume = {142}, journal = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, number = {4}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-9606}, doi = {10.1063/1.4905603}, pages = {9}, year = {2015}, abstract = {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.}, language = {en} } @article{SchreckPietzschKunnusetal.2014, author = {Schreck, Simon and Pietzsch, Annette and Kunnus, Kristjan and Kennedy, Brian and Quevedo, Wilson and Miedema, Piter S. and Wernet, Philippe and F{\"o}hlisch, Alexander}, title = {Dynamics of the OH group and the electronic structure of liquid alcohols}, series = {Structural dynamics}, volume = {1}, journal = {Structural dynamics}, number = {5}, publisher = {American Institute of Physics}, address = {Melville}, issn = {2329-7778}, doi = {10.1063/1.4897981}, pages = {14}, year = {2014}, abstract = {In resonant inelastic soft x-ray scattering (RIXS) from molecular and liquid systems, the interplay of ground state structural and core-excited state dynamical contributions leads to complex spectral shapes that partially allow for ambiguous interpretations. In this work, we dissect these contributions in oxygen K-edge RIXS from liquid alcohols. We use the scattering into the electronic ground state as an accurate measure of nuclear dynamics in the intermediate core-excited state of the RIXS process. We determine the characteristic time in the core-excited state until nuclear dynamics give a measurable contribution to the RIXS spectral profiles to tau(dyn) = 1.2 +/- 0.8 fs. By detuning the excitation energy below the absorption resonance we reduce the effective scattering time below sdyn, and hence suppress these dynamical contributions to a minimum. From the corresponding RIXS spectra of liquid methanol, we retrieve the "dynamic-free" density of states and find that it is described solely by the electronic states of the free methanol molecule. From this and from the comparison of normal and deuterated methanol, we conclude that the split peak structure found in the lone-pair emission region at non-resonant excitation originates from dynamics in the O-H bond in the core-excited state. We find no evidence that this split peak feature is a signature of distinct ground state structural complexes in liquid methanol. However, we demonstrate how changes in the hydrogen bond coordination within the series of linear alcohols from methanol to hexanol affect the split peak structure in the liquid alcohols. (C) 2014 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.}, language = {en} }