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Anomalous Behavior of the Homogeneous Ice Nucleation Rate in No-Man's Land
Stockholm University, Faculty of Science, Department of Physics. SLAC National Accelerator Laboratory, USA.
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Number of Authors: 21
2015 (English)In: Journal of Physical Chemistry Letters, ISSN 1948-7185, E-ISSN 1948-7185, Vol. 6, no 14, 2826-2832 p.Article in journal (Refereed) Published
Abstract [en]

We present an analysis of ice nucleation kinetics from near-ambient pressure water as temperature decreases below the homogeneous limit T-H by cooling micrometer-sized droplets (microdroplets) evaporatively at 10(3)-10(4) K/s and probing the structure ultrafast using femtosecond pulses from the Linac Coherent Light Source (LCLS) free-electron X-ray laser. Below 232 K, we observed a slower nucleation rate increase with decreasing temperature than anticipated from previous measurements, which we suggest is due to the rapid decrease in water's diffusivity. This is consistent with earlier findings that microdroplets do not crystallize at <227 K, but vitrify at cooling rates of 10(6)-10(7) K/s. We also hypothesize that the slower increase in the nucleation rate is connected with the proposed fragile-to-strong transition anomaly in water.

Place, publisher, year, edition, pages
2015. Vol. 6, no 14, 2826-2832 p.
National Category
Chemical Sciences Nano Technology Physical Sciences
Research subject
Theoretical Physics
URN: urn:nbn:se:su:diva-119545DOI: 10.1021/acs.jpclett.5b01164ISI: 000358339600028OAI: diva2:847430
Available from: 2015-08-20 Created: 2015-08-17 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

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Sellberg, Jonas A.Schlesinger, DanielArnann-Winkel, KatrinPettersson, Lars G. M.Nilsson, Anders
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