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Relationship between x-ray emission and absorption spectroscopy and the local H-bond environment in water

Zhovtobriukh, Iurii; Besley, Nicholas A.; Fransson, Thomas; Nilsson, Anders; Pettersson, Lars G.M.

Authors

Iurii Zhovtobriukh

Nicholas A. Besley

Thomas Fransson

Anders Nilsson

Lars G.M. Pettersson



Abstract

The connection between specific spectrum features in the water X-ray absorption (XAS) and X-ray emission (XES) spectra 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 (1b1) 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 characterised by high LSI values and two strong donated and two strong accepted H-bonds contribute to the low energy 1b1 emission peak and to the post-edge region in absorption. Molecules with asymmetric H-bond environment with one strong accepted and one strong donated H-bond and low LSI values give rise to the high energy 1b1 peak in the emission spectrum and mainly contribute to the pre-edge and main-edge in the absorption spectrum. The 1b1 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 Å) and for very asymmetric structures elongated H-bonds (longer than 2.8 Å). Such structures are present, but underrepresented, in the simulations which give more of an average of the two extremes.

Citation

Zhovtobriukh, I., Besley, N. A., Fransson, T., Nilsson, A., & Pettersson, L. G. (2018). Relationship between x-ray emission and absorption spectroscopy and the local H-bond environment in water. Journal of Chemical Physics, 148(14), Article 144507. https://doi.org/10.1063/1.5009457

Journal Article Type Article
Acceptance Date Mar 9, 2018
Publication Date Apr 10, 2018
Deposit Date Mar 21, 2018
Publicly Available Date Mar 29, 2024
Journal Journal of Chemical Physics
Print ISSN 0021-9606
Electronic ISSN 1089-7690
Publisher American Institute of Physics
Peer Reviewed Peer Reviewed
Volume 148
Issue 14
Article Number 144507
DOI https://doi.org/10.1063/1.5009457
Public URL https://nottingham-repository.worktribe.com/output/924635
Publisher URL https://aip.scitation.org/doi/full/10.1063/1.5009457
Additional Information This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. The following article appeared in Iurii Zhovtobriukh, Nicholas A. Besley,Thomas Fransson, Anders Nilsson, and Lars G. M. Pettersson Relationship between x-ray emission and absorption spectroscopy and the local H-bond environment in water The Journal of Chemical Physics 2018 148:14 and may be found at https://aip.scitation.org/doi/full/10.1063/1.5009457

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