TY - JOUR A1 - Niskanen, Johannes A1 - Fondell, Mattis A1 - Sahle, Christoph J. A1 - Eckert, Sebastian A1 - Jay, Raphael Martin A1 - Gilmore, Keith A1 - Pietzsch, Annette A1 - Dantz, Marcus A1 - Lu, Xingye A1 - McNally, Daniel E. A1 - Schmitt, Thorsten A1 - Vaz da Cruz, Vinicius A1 - Kimberg, Victor A1 - Föhlisch, Alexander A1 - Gel’mukhanov, Faris T1 - Compatibility of quantitative X-ray spectroscopy with continuous distribution models of water at ambient conditions JF - Proceedings of the National Academy of Sciences of the United States of America N2 - The phase diagram of water harbors controversial views on underlying structural properties of its constituting molecular moieties, its fluctuating hydrogen-bonding network, as well as pair-correlation functions. In this work, long energy-range detection of the X-ray absorption allows us to unambiguously calibrate the spectra for water gas, liquid, and ice by the experimental atomic ionization cross-section. In liquid water, we extract the mean value of 1.74 +/- 2.1% donated and accepted hydrogen bonds per molecule, pointing to a continuous-distribution model. In addition, resonant inelastic X-ray scattering with unprecedented energy resolution also supports continuous distribution of molecular neighborhoods within liquid water, as do X-ray emission spectra once the femtosecond scattering duration and proton dynamics in resonant X-ray-matter interaction are taken into account. Thus, X-ray spectra of liquid water in ambient conditions can be understood without a two-structure model, whereas the occurrence of nanoscale-length correlations within the continuous distribution remains open. KW - structure of water KW - X-ray spectroscopy KW - continuous distribution model Y1 - 2019 U6 - https://doi.org/10.1073/pnas.1815701116 SN - 0027-8424 VL - 116 IS - 10 SP - 4058 EP - 4063 PB - National Acad. of Sciences CY - Washington ER - TY - GEN A1 - Niskanen, Johannes A1 - Fondell, Mattis A1 - Sahle, Christoph J. A1 - Eckert, Sebastian A1 - Jay, Raphael Martin A1 - Gilmore, Keith A1 - Pietzsch, Annette A1 - Dantz, Marcus A1 - Lu, Xingye A1 - McNally, Daniel E. A1 - Schmitt, Thorsten A1 - Vaz da Cruz, Vinicius A1 - Kimberg, Victor A1 - Föhlisch, Alexander T1 - Reply to Pettersson et al.: Why X-ray spectral features are compatible to continuous distribution models in ambient water T2 - Proceedings of the National Academy of Sciences of the United States of America Y1 - 2019 U6 - https://doi.org/10.1073/pnas.1909551116 SN - 0027-8424 VL - 116 IS - 35 SP - 17158 EP - 17159 PB - National Acad. of Sciences CY - Washington ER - TY - JOUR A1 - Niskanen, Johannes A1 - Sahle, Christoph J. A1 - Gilmore, Keith A1 - Uhlig, Frank A1 - Smiatek, Jens A1 - Föhlisch, Alexander T1 - Disentangling structural information from core-level excitation spectra JF - Physical review : E, Statistical, nonlinear and soft matter physics N2 - Core-level spectra of liquids can be difficult to interpret due to the presence of a range of local environments. We present computational methods for investigating core-level spectra based on the idea that both local structural parameters and the x-ray spectra behave as functions of the local atomic configuration around the absorbing site. We identify correlations between structural parameters and spectral intensities in defined regions of interest, using the oxygen K-edge excitation spectrum of liquid water as a test case. Our results show that this kind of analysis can find the main structure-spectral relationships of ice, liquid water, and supercritical water. Y1 - 2017 U6 - https://doi.org/10.1103/PhysRevE.96.013319 SN - 2470-0045 SN - 2470-0053 VL - 96 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Sahle, Christoph J. A1 - Niskanen, Johannes A1 - Schmidt, Christian A1 - Stefanski, Johannes A1 - Gilmore, Keith A1 - Forov, Yury A1 - Jahn, Sandro A1 - Wilke, Max A1 - Sternemann, Christian T1 - Cation Hydration in Supercritical NaOH and HCl Aqueous Solutions JF - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry N2 - We present a study of the local atomic environment of the oxygen atoms in the aqueous solutions of NaOH and HCl under simultaneous high-temperature and high-pressure conditions. Experimental nonresonant X-ray Raman scattering core-level spectra at the oxygen K-edge show systematic changes as a function of temperature and pressure. These systematic changes are distinct for the two different solutes and are described well by calculations within the Bethe- Salpeter formalism for snapshots from ab initio molecular dynamics simulations. The agreement between experimental and simulation results allows us to use the computations for a detailed fingerprinting analysis in an effort to elucidate the local atomic structure and hydrogen-bonding topology in these relevant solutions. We observe that both electrolytes, especially NaOH, enhance hydrogen bonding and tetrahedrality in the water structure at supercritical conditions, in particular in the vicinity of the hydration shells. This effect is accompanied with the association of the HCl and NaOH molecules at elevated temperatures. Y1 - 2017 U6 - https://doi.org/10.1021/acs.jpcb.7b09688 SN - 1520-6106 VL - 121 SP - 11383 EP - 11389 PB - American Chemical Society CY - Washington ER - TY - GEN A1 - Spiekermann, Georg A1 - Harder, M. A1 - Gilmore, Keith A1 - Zalden, Peter A1 - Sahle, Christoph J. A1 - Petitgirard, Sylvain A1 - Wilke, Max A1 - Biedermann, Nicole A1 - Weis, Thomas A1 - Morgenroth, Wolfgang A1 - Tse, John S. A1 - Kulik, E. A1 - Nishiyama, Norimasa A1 - Yavaş, Hasan A1 - Sternemann, Christian T1 - Persistent Octahedral Coordination in Amorphous GeO₂ Up to 100 GPa by Kβ'' X-Ray Emission Spectroscopy T2 - Postprints der Universität Potsdam Mathematisch-Naturwissenschaftliche Reihe N2 - We measure valence-to-core x-ray emission spectra of compressed crystalline GeO₂ up to 56 GPa and of amorphous GeO₂ up to 100 GPa. In a novel approach, we extract the Ge coordination number and mean Ge-O distances from the emission energy and the intensity of the Kβ'' emission line. The spectra of high-pressure polymorphs are calculated using the Bethe-Salpeter equation. Trends observed in the experimental and calculated spectra are found to match only when utilizing an octahedral model. The results reveal persistent octahedral Ge coordination with increasing distortion, similar to the compaction mechanism in the sequence of octahedrally coordinated crystalline GeO₂ high-pressure polymorphs. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 699 KW - rutile-type KW - glass KW - crystalline KW - pressures KW - complexes KW - silicon KW - oxygen KW - SIO₂ KW - MO KW - CU Y1 - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-427755 SN - 1866-8372 IS - 699 ER - TY - JOUR A1 - Spiekermann, Georg A1 - Harder, M. A1 - Gilmore, Keith A1 - Zalden, Peter A1 - Sahle, Christoph J. A1 - Petitgirard, Sylvain A1 - Wilke, Max A1 - Biedermann, Nicole A1 - Weis, Thomas A1 - Morgenroth, Wolfgang A1 - Tse, John S. A1 - Kulik, E. A1 - Nishiyama, Norimasa A1 - Yavaş, Hasan A1 - Sternemann, Christian T1 - Persistent Octahedral Coordination in Amorphous GeO₂ Up to 100 GPa by Kβ'' X-Ray Emission Spectroscopy JF - Physical Review X N2 - We measure valence-to-core x-ray emission spectra of compressed crystalline GeO₂ up to 56 GPa and of amorphous GeO₂ up to 100 GPa. In a novel approach, we extract the Ge coordination number and mean Ge-O distances from the emission energy and the intensity of the Kβ'' emission line. The spectra of high-pressure polymorphs are calculated using the Bethe-Salpeter equation. Trends observed in the experimental and calculated spectra are found to match only when utilizing an octahedral model. The results reveal persistent octahedral Ge coordination with increasing distortion, similar to the compaction mechanism in the sequence of octahedrally coordinated crystalline GeO₂ high-pressure polymorphs. KW - rutile-type KW - glass KW - crystalline KW - pressures KW - complexes KW - silicon KW - oxygen KW - SIO₂ KW - MO KW - CU Y1 - 2019 U6 - https://doi.org/10.1103/PhysRevX.9.011025 SN - 2469-9926 SN - 0556-2791 SN - 1050-2947 SN - 1094-1622 VL - 9 IS - 1 PB - American Physical Society by the American Institute of Physics CY - Melville, NY ER -