- 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 andWe 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.…
MetadatenVerfasserangaben: | Christoph J. Sahle, Johannes Niskanen, Christian SchmidtORCiD, Johannes Stefanski, Keith Gilmore, Yury Forov, Sandro JahnORCiD, Max WilkeORCiDGND, Christian Sternemann |
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DOI: | https://doi.org/10.1021/acs.jpcb.7b09688 |
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ISSN: | 1520-6106 |
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Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/29160070 |
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Titel des übergeordneten Werks (Englisch): | The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry |
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Verlag: | American Chemical Society |
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Verlagsort: | Washington |
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Publikationstyp: | Wissenschaftlicher Artikel |
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Sprache: | Englisch |
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Jahr der Erstveröffentlichung: | 2017 |
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Erscheinungsjahr: | 2017 |
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Datum der Freischaltung: | 20.04.2020 |
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Band: | 121 |
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Seitenanzahl: | 7 |
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Erste Seite: | 11383 |
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Letzte Seite: | 11389 |
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Fördernde Institution: | Cluster of Excellence RESOLV - DFG [EXC 1069]; Deutsche Forschungsgemeinschaft |
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Organisationseinheiten: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Geowissenschaften |
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Peer Review: | Referiert |
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Name der Einrichtung zum Zeitpunkt der Publikation: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Erd- und Umweltwissenschaften |
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