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

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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.


  • Jonas A Sellberg
  • Trevor A McQueen
  • Hartawan Laksmono
  • Simon Schreck
  • Martin Beye
  • Daniel P DePonte
  • Brian Kennedy
  • Dennis Nordlund
  • Raymond G Sierra
  • Daniel Schlesinger
  • Takashi Tokushima
  • Iurii Zhovtobriukh
  • Sebastian Eckert
  • Vegard H Segtnan
  • Hirohito Ogasawara
  • Katharina Kubicek
  • Simone Techert
  • Uwe Bergmann
  • Georgi L Dakovski
  • William F Schlotter
  • And 6 others
  • Yoshihisa Harada
  • Michael J Bogan
  • Philippe Wernet
  • Alexander Föhlisch
  • Lars G M Pettersson
  • Anders Nilsson
Research areas and keywords

Subject classification (UKÄ) – MANDATORY

  • Physical Sciences
  • Natural Sciences
Original languageEnglish
Article number044505
JournalJournal of Chemical Physics
Issue number4
Publication statusPublished - 2015
Publication categoryResearch