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Relationship between x-ray emission and absorption spectroscopy and the local H-bond environment in water
Stockholm University, Faculty of Science, Department of Physics.
Stockholm University, Faculty of Science, Department of Physics.
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Number of Authors: 52018 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 148, no 14, article id 144507Article in journal (Refereed) Published
Abstract [en]

The connection between specific features in the water X-ray absorption spectrum and X-ray emission spectrum (XES) and the local H-bond coordination is studied based on structures obtained from path-integral molecular dynamics simulations using either the opt-PBE-vdW density functional or the MB-pol force field. Computing the XES spectrum using all molecules in a snapshot results in only one peak in the lone-pair (1b(1)) region, while the experiment shows two peaks separated by 0.8-0.9 eV. Different H-bond configurations were classified based on the local structure index (LSI) and a geometrical H-bond cone criterion. We find that tetrahedrally coordinated molecules characterized by high LSI values and two strong donated and two strong accepted H-bonds contribute to the lowenergy 1b(1) emission peak and to the post-edge region in absorption. Molecules with the asymmetric H-bond environment with one strong accepted H-bond and one strong donated H-bond and low LSI values give rise to the high energy 1b(1) peak in the emission spectrum and mainly contribute to the pre-edge and main-edge in the absorption spectrum. The 1b(1) peak splitting can be increased to 0.62 eV by imposing constraints on the H-bond length, i.e., for very tetrahedral structures short H-bonds (less than 2.68 angstrom) and for very asymmetric structures elongated H-bonds (longer than 2.8 angstrom). Such structures are present, but under-represented, in the simulations which give more of an average of the two extremes.

Place, publisher, year, edition, pages
2018. Vol. 148, no 14, article id 144507
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Chemical Sciences Physical Sciences
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URN: urn:nbn:se:su:diva-155902DOI: 10.1063/1.5009457ISI: 000430128600033PubMedID: 29655333OAI: oai:DiVA.org:su-155902DiVA, id: diva2:1202777
Available from: 2018-04-30 Created: 2018-04-30 Last updated: 2018-04-30Bibliographically approved

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Zhovtobriukh, IuriiNilsson, AndersPettersson, Lars G. M.
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