Relationship between x-ray emission and absorption spectroscopy and the local H-bond environment in water
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...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
American Institute of Physics
2018
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| Online Access: | https://eprints.nottingham.ac.uk/50560/ |
| _version_ | 1848798283147771904 |
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| author | Zhovtobriukh, Iurii Besley, Nicholas A. Fransson, Thomas Nilsson, Anders Pettersson, Lars G.M. |
| author_facet | Zhovtobriukh, Iurii Besley, Nicholas A. Fransson, Thomas Nilsson, Anders Pettersson, Lars G.M. |
| author_sort | Zhovtobriukh, Iurii |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | 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. |
| first_indexed | 2025-11-14T20:17:18Z |
| format | Article |
| id | nottingham-50560 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-14T20:17:18Z |
| publishDate | 2018 |
| publisher | American Institute of Physics |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-505602020-05-08T12:00:23Z https://eprints.nottingham.ac.uk/50560/ 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. 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. American Institute of Physics 2018-04-10 Article PeerReviewed application/pdf en https://eprints.nottingham.ac.uk/50560/1/final-submitted.pdf Zhovtobriukh, Iurii, Besley, Nicholas A., Fransson, Thomas, Nilsson, Anders and Pettersson, Lars G.M. (2018) Relationship between x-ray emission and absorption spectroscopy and the local H-bond environment in water. Journal of Chemical Physics, 148 (14). 144507/1-144507/. ISSN 1089-7690 https://aip.scitation.org/doi/full/10.1063/1.5009457 doi:10.1063/1.5009457 doi:10.1063/1.5009457 |
| spellingShingle | Zhovtobriukh, Iurii Besley, Nicholas A. Fransson, Thomas Nilsson, Anders Pettersson, Lars G.M. Relationship between x-ray emission and absorption spectroscopy and the local H-bond environment in water |
| title | Relationship between x-ray emission and absorption spectroscopy and the local H-bond environment in water |
| title_full | Relationship between x-ray emission and absorption spectroscopy and the local H-bond environment in water |
| title_fullStr | Relationship between x-ray emission and absorption spectroscopy and the local H-bond environment in water |
| title_full_unstemmed | Relationship between x-ray emission and absorption spectroscopy and the local H-bond environment in water |
| title_short | Relationship between x-ray emission and absorption spectroscopy and the local H-bond environment in water |
| title_sort | relationship between x-ray emission and absorption spectroscopy and the local h-bond environment in water |
| url | https://eprints.nottingham.ac.uk/50560/ https://eprints.nottingham.ac.uk/50560/ https://eprints.nottingham.ac.uk/50560/ |