Change search
ReferencesLink to record
Permanent link

Direct link
X-ray emission spectroscopy of bulk liquid water in no-man's land
Stockholm University, Faculty of Science, Department of Physics. SLAC National Accelerator Laboratory, USA.
Show others and affiliations
2015 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 142, no 4, 044505Article in journal (Refereed) Published
Abstract [en]

The structure of bulk liquid water was recently probed by x-ray scattering below the temperature limit of homogeneous nucleation (T-H) of similar to 232 K [J. A. Sellberg et al., Nature 510, 381-384 (2014)]. Here, we utilize a similar approach to study the structure of bulk liquid water below T-H using oxygen K-edge x-ray emission spectroscopy (XES). Based on previous XES experiments [T. Tokushima et al., Chem. Phys. Lett. 460, 387-400 (2008)] at higher temperatures, we expected the ratio of the 1b(1)' and 1b(1) peaks associated with the lone-pair orbital in water to change strongly upon deep supercooling as the coordination of the hydrogen (H-) bonds becomes tetrahedral. In contrast, we observed only minor changes in the lone-pair spectral region, challenging an interpretation in terms of two interconverting species. A number of alternative hypotheses to explain the results are put forward and discussed. Although the spectra can be explained by various contributions from these hypotheses, we here emphasize the interpretation that the line shape of each component changes dramatically when approaching lower temperatures, where, in particular, the peak assigned to the proposed disordered component would become more symmetrical as vibrational interference becomes more important.

Place, publisher, year, edition, pages
2015. Vol. 142, no 4, 044505
National Category
Physical Sciences Chemical Sciences
URN: urn:nbn:se:su:diva-115298DOI: 10.1063/1.4905603ISI: 000349018100034PubMedID: 25637993OAI: diva2:800091


Available from: 2015-04-01 Created: 2015-03-18 Last updated: 2015-09-18Bibliographically approved
In thesis
1. X-ray scattering and spectroscopy of supercooled water and ice
Open this publication in new window or tab >>X-ray scattering and spectroscopy of supercooled water and ice
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis presents experimental studies of water and ice at near-atmospheric pressures using intense x-rays only accessible at synchrotrons and free-electron lasers. In particular, it focuses on the deeply supercooled, metastable state and its implications on ice nucleation.

The local structure of the liquid phase was studied by x-ray scattering over a wide temperature range extending from 339 K down to 227 K. In order to be able to study the deeply supercooled liquid, micron-sized water droplets were evaporatively cooled in vacuum and probed by ultrashort x-ray pulses. This is to date the lowest temperature at which measurements of the structure have been performed on bulk liquid water cooled from room temperature. Upon deep supercooling, the structure evolved toward that of a low-density liquid with local tetrahedral coordination. At ~230 K, where the low-density liquid structure started to dominate, the number of droplets containing ice nuclei increased rapidly. The estimated nucleation rate suggests that there is a “fragile-to-strong” transition in the dynamics of the liquid below 230 K, and its implications on water structure are discussed.

Similarly, the electronic structure of deeply supercooled water was studied by x-ray emission spectroscopy down to 222 K, but the spectral changes expected from the structural transformation remained absent and explanations are discussed. At high fluence, the non-linear dependence of the x-ray emission yield indicated that there were high valence hole densities created during the x-ray pulse length due to Auger cascades, resulting in reabsorption of the x-ray emission.

Finally, the hydrogen-bonded network in water was studied by x-ray absorption spectroscopy and compared to various ices. It was found that the pre-edge absorption cross-section, which is associated with distorted hydrogen bonds, could be minimized for crystalline ice grown on a hydrophobic BaF2(111) surface with low concentration of nucleation centers.

Place, publisher, year, edition, pages
Stockholm: Department of Physics, Stockholm Univeristy, 2014. 148 p.
supercooled water, ice, x-ray scattering, x-ray spectroscopy, free-electron laser
National Category
Physical Chemistry
Research subject
Chemical Physics
urn:nbn:se:su:diva-103009 (URN)978–91–7447–902–7 (ISBN)
Public defence
2014-05-30, FA32, AlbaNova Universitetscentrum, Roslagstullsbacken 21, Stockholm, 10:15 (English)

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 3: Manuscript. Paper 4: Manuscript. Paper 5: Manuscript. Paper 6: Manuscript.

Available from: 2014-05-08 Created: 2014-04-26 Last updated: 2015-09-18Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full textPubMed

Search in DiVA

By author/editor
Sellberg, Jonas A.Schlesinger, DanielZhovtobriukh, IuriiPettersson, Lars G. M.Nilsson, Anders
By organisation
Department of Physics
In the same journal
Journal of Chemical Physics
Physical SciencesChemical Sciences

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 25 hits
ReferencesLink to record
Permanent link

Direct link