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X-ray emission spectroscopy of bulk liquid water in "no-man's land".

Sellberg, Jonas A; McQueen, Trevor A; Laksmono, Hartawan; Schreck, Simon; Beye, Martin; DePonte, Daniel P; Kennedy, Brian LU ; Nordlund, Dennis; Sierra, Raymond G and Schlesinger, Daniel, et al. (2015) In Journal of Chemical Physics 142(4).
Abstract
The structure of bulk liquid water was recently probed by x-ray scattering below the temperature limit of homogeneous nucleation (TH) of ∼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 TH 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 1b1' and 1b1″ 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,... (More)
The structure of bulk liquid water was recently probed by x-ray scattering below the temperature limit of homogeneous nucleation (TH) of ∼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 TH 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 1b1' and 1b1″ 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. (Less)
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Journal of Chemical Physics
volume
142
issue
4
publisher
American Institute of Physics
external identifiers
  • pmid:25637993
  • wos:000349018100034
  • scopus:84923792133
ISSN
0021-9606
DOI
10.1063/1.4905603
language
English
LU publication?
yes
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182c04e4-9b8c-4918-8d96-461e549c6f99 (old id 5145769)
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2015-03-09 14:29:48
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2017-10-01 03:12:15
@article{182c04e4-9b8c-4918-8d96-461e549c6f99,
  abstract     = {The structure of bulk liquid water was recently probed by x-ray scattering below the temperature limit of homogeneous nucleation (TH) of ∼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 TH 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 1b1' and 1b1″ 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.},
  articleno    = {044505},
  author       = {Sellberg, Jonas A and McQueen, Trevor A and Laksmono, Hartawan and Schreck, Simon and Beye, Martin and DePonte, Daniel P and Kennedy, Brian and Nordlund, Dennis and Sierra, Raymond G and Schlesinger, Daniel and Tokushima, Takashi and Zhovtobriukh, Iurii and Eckert, Sebastian and Segtnan, Vegard H and Ogasawara, Hirohito and Kubicek, Katharina and Techert, Simone and Bergmann, Uwe and Dakovski, Georgi L and Schlotter, William F and Harada, Yoshihisa and Bogan, Michael J and Wernet, Philippe and Föhlisch, Alexander and Pettersson, Lars G M and Nilsson, Anders},
  issn         = {0021-9606},
  language     = {eng},
  number       = {4},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {X-ray emission spectroscopy of bulk liquid water in "no-man's land".},
  url          = {http://dx.doi.org/10.1063/1.4905603},
  volume       = {142},
  year         = {2015},
}