TY - JOUR A1 - Arhammar, C. A1 - Pietzsch, Annette A1 - Bock, Nicolas A1 - Holmstroem, Erik A1 - Araujo, C. Moyses A1 - Grasjo, Johan A1 - Zhao, Shuxi A1 - Green, Sara A1 - Peery, T. A1 - Hennies, Franz A1 - Amerioun, Shahrad A1 - Föhlisch, Alexander A1 - Schlappa, Justine A1 - Schmitt, Thorsten A1 - Strocov, Vladimir N. A1 - Niklasson, Gunnar A. A1 - Wallace, Duane C. A1 - Rubensson, Jan-Erik A1 - Johansson, Borje A1 - Ahuja, Rajeev C. T1 - Unveiling the complex electronic structure of amorphous metal oxides JF - Proceedings of the National Academy of Sciences of the United States of America N2 - Amorphous materials represent a large and important emerging area of material's science. Amorphous oxides are key technological oxides in applications such as a gate dielectric in Complementary metal-oxide semiconductor devices and in Silicon-Oxide-Nitride-Oxide-Silicon and TANOS (TaN-Al2O3-Si3N4-SiO2-Silicon) flash memories. These technologies are required for the high packing density of today's integrated circuits. Therefore the investigation of defect states in these structures is crucial. In this work we present X-ray synchrotron measurements, with an energy resolution which is about 5-10 times higher than is attainable with standard spectrometers, of amorphous alumina. We demonstrate that our experimental results are in agreement with calculated spectra of amorphous alumina which we have generated by stochastic quenching. This first principles method, which we have recently developed, is found to be superior to molecular dynamics in simulating the rapid gas to solid transition that takes place as this material is deposited for thin film applications. We detect and analyze in detail states in the band gap that originate from oxygen pairs. Similar states were previously found in amorphous alumina by other spectroscopic methods and were assigned to oxygen vacancies claimed to act mutually as electron and hole traps. The oxygen pairs which we probe in this work act as hole traps only and will influence the information retention in electronic devices. In amorphous silica oxygen pairs have already been found, thus they may be a feature which is characteristic also of other amorphous metal oxides. KW - stochastic quench KW - X-ray absorption spectroscopy KW - ab initio KW - coating Y1 - 2011 U6 - https://doi.org/10.1073/pnas.1019698108 SN - 0027-8424 VL - 108 IS - 16 SP - 6355 EP - 6360 PB - National Acad. of Sciences CY - Washington ER - TY - JOUR A1 - Born, Artur A1 - Decker, Regis A1 - Haverkamp, Robert A1 - Ruotsalainen, Kari A1 - Bauer, Karl A1 - Pietzsch, Annette A1 - Föhlisch, Alexander A1 - Büchner, Robby T1 - Thresholding of the Elliott-Yafet spin-flip scattering in multi-sublattice magnets by the respective exchange energies JF - Scientific reports N2 - How different microscopic mechanisms of ultrafast spin dynamics coexist and interplay is not only relevant for the development of spintronics but also for the thorough description of physical systems out-of-equilibrium. In pure crystalline ferromagnets, one of the main microscopic mechanism of spin relaxation is the electron-phonon (el-ph) driven spin-flip, or Elliott-Yafet, scattering. Unexpectedly, recent experiments with ferro- and ferrimagnetic alloys have shown different dynamics for the different sublattices. These distinct sublattice dynamics are contradictory to the Elliott-Yafet scenario. In order to rationalize this discrepancy, it has been proposed that the intra- and intersublattice exchange interaction energies must be considered in the microscopic demagnetization mechanism, too. Here, using a temperature-dependent x-ray emission spectroscopy (XES) method, we address experimentally the element specific el-ph angular momentum transfer rates, responsible for the spin-flips in the respective (sub)lattices of Fe20Ni80, Fe50Ni50 and pure nickel single crystals. We establish how the deduced rate evolution with the temperature is linked to the exchange coupling constants reported for different alloy stoichiometries and how sublattice exchange energies threshold the related el-ph spin-flip channels. Thus, these results evidence that the Elliott-Yafet spin-flip scattering, thresholded by sublattice exchange energies, is the relevant microscopic process to describe sublattice dynamics in alloys and elemental magnetic systems. Y1 - 2021 U6 - https://doi.org/10.1038/s41598-021-81177-9 SN - 2045-2322 VL - 11 IS - 1 PB - Springer Nature CY - Berlin 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 - 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 - Couto, Rafael C. A1 - Cruz, Vinicius V. A1 - Ertan, Emelie A1 - Eckert, Sebastian A1 - Fondell, Mattis A1 - Dantz, Marcus A1 - Kennedy, Brian A1 - Schmitt, Thorsten A1 - Pietzsch, Annette A1 - Guimaraes, Freddy F. A1 - Agren, Hans A1 - Odelius, Michael A1 - Kimberg, Victor A1 - Föhlisch, Alexander T1 - Selective gating to vibrational modes through resonant X-ray scattering JF - Nature Communications N2 - The dynamics of fragmentation and vibration of molecular systems with a large number of coupled degrees of freedom are key aspects for understanding chemical reactivity and properties. Here we present a resonant inelastic X-ray scattering (RIXS) study to show how it is possible to break down such a complex multidimensional problem into elementary components. Local multimode nuclear wave packets created by X-ray excitation to different core-excited potential energy surfaces (PESs) will act as spatial gates to selectively probe the particular ground-state vibrational modes and, hence, the PES along these modes. We demonstrate this principle by combining ultra-high resolution RIXS measurements for gas-phase water with state-of-the-art simulations. Y1 - 2017 U6 - https://doi.org/10.1038/ncomms14165 SN - 2041-1723 VL - 8 PB - Nature Publ. Group CY - London ER - TY - GEN A1 - Couto, Rafael C. A1 - Cruz, Vinicius V. A1 - Ertan, Emelie A1 - Eckert, Sebastian A1 - Fondell, Mattis A1 - Dantz, Marcus A1 - Kennedy, Brian A1 - Schmitt, Thorsten A1 - Pietzsch, Annette A1 - Guimarães, Freddy F. A1 - Ågren, Hans A1 - Gel’mukhanov, Faris A1 - Odelius, Michael A1 - Kimberg, Victor A1 - Föhlisch, Alexander T1 - Selective gating to vibrational modes through resonant X-ray scattering T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - The dynamics of fragmentation and vibration of molecular systems with a large number of coupled degrees of freedom are key aspects for understanding chemical reactivity and properties. Here we present a resonant inelastic X-ray scattering (RIXS) study to show how it is possible to break down such a complex multidimensional problem into elementary components. Local multimode nuclear wave packets created by X-ray excitation to different core-excited potential energy surfaces (PESs) will act as spatial gates to selectively probe the particular ground-state vibrational modes and, hence, the PES along these modes. We demonstrate this principle by combining ultra-high resolution RIXS measurements for gas-phase water with state-of-the-art simulations. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1124 KW - potential-energy surface KW - raman-scattering KW - water-vapor KW - spectroscopy KW - chemistry KW - molecule KW - spectrum KW - CM(-1) KW - states KW - NM Y1 - 2021 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-436926 SN - 1866-8372 IS - 1124 ER - TY - JOUR A1 - Decker, Regis A1 - Born, Artur A1 - Ruotsalainen, Kari A1 - Bauer, Karl A1 - Haverkamp, Robert A1 - Büchner, Robby A1 - Pietzsch, Annette A1 - Föhlisch, Alexander T1 - Spin-lattice angular momentum transfer of localized and valence electrons in the demagnetization transient state of gadolinium JF - Applied physics letters N2 - The electron-phonon scattering is one of the main microscopic mechanisms responsible for the spin-flip in the transient state of ultrafast demagnetization. Here, we present an experimental determination of the temperature-dependent electron-phonon scattering rate in Gd. Using a static x-ray emission spectroscopy method, where the reduction of the decay peak intensities when increasing the temperature is quantified, we measure independently the electron-phonon scattering rate for the 5d and the 4f electrons. We deduce the temperature dependence of scattering for the 5d electrons, while no effect on the phonon population is observed for the 4f electrons. Our results suggest that the ultrafast magnetization dynamics in Gd is triggered by the spin-flip in the 5d electrons. We also evidence the existence of a temperature threshold, above which spin-flip scattering of the 5d electrons takes place. We deduce that during the transient state of ultrafast demagnetization, the exchange energy between 5d electrons has to be overcome before the microscopic electron-phonon scattering process can occur. Y1 - 2021 U6 - https://doi.org/10.1063/5.0063404 SN - 0003-6951 SN - 1077-3118 VL - 119 IS - 15 PB - AIP Publishing CY - Melville 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 - Eckert, Sebastian A1 - Beye, Martin A1 - Pietzsch, Annette A1 - Quevedo, Wilson A1 - Hantschmann, Markus A1 - Ochmann, Miguel A1 - Ross, Matthew A1 - Minitti, Michael P. A1 - Turner, Joshua J. A1 - Moeller, Stefan P. A1 - Schlotter, William F. A1 - Dakovski, Georgi L. A1 - Khalil, Munira A1 - Huse, Nils A1 - Föhlisch, Alexander T1 - Principles of femtosecond X-ray/optical cross-correlation with X-ray induced transient optical reflectivity in solids JF - Applied physics letters N2 - The discovery of ultrafast X-ray induced optical reflectivity changes enabled the development of X-ray/optical cross correlation techniques at X-ray free electron lasers worldwide. We have now linked through experiment and theory the fundamental excitation and relaxation steps with the transient optical properties in finite solid samples. Therefore, we gain a thorough interpretation and an optimized detection scheme of X-ray induced changes to the refractive index and the X-ray/optical cross correlation response. (C) 2015 AIP Publishing LLC. Y1 - 2015 U6 - https://doi.org/10.1063/1.4907949 SN - 0003-6951 SN - 1077-3118 VL - 106 IS - 6 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Eckert, Sebastian A1 - Mascarenhas, Eric Johnn A1 - Mitzner, Rolf A1 - Jay, Raphael Martin A1 - Pietzsch, Annette A1 - Fondell, Mattis A1 - Vaz da Cruz, Vinicius A1 - Föhlisch, Alexander T1 - From the free ligand to the transition metal complex BT - FeEDTA(-) formation seen at ligand K-Edges JF - Inorganic chemistry N2 - Chelating agents are an integral part of transition metal complex chemistry with broad biological and industrial relevance. The hexadentate chelating agent ethylenediaminetetraacetic acid (EDTA) has the capability to bind to metal ions at its two nitrogen and four of its carboxylate oxygen sites. We use resonant inelastic X-ray scattering at the 1s absorption edge of the aforementioned elements in EDTA and the iron(III)-EDTA complex to investigate the impact of the metal-ligand bond formation on the electronic structure of EDTA. Frontier orbital distortions, occupation changes, and energy shifts through metal- ligand bond formation are probed through distinct spectroscopic signatures. KW - Energy KW - Ligands KW - Metals KW - Nitrogen KW - Oxygen Y1 - 2022 U6 - https://doi.org/10.1021/acs.inorgchem.2c00789 SN - 0020-1669 SN - 1520-510X VL - 61 IS - 27 SP - 10321 EP - 10328 PB - American Chemical Society CY - Washington ER -