• search hit 6 of 27
Back to Result List

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

  • 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 thatThe 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. (C) 2015 AIP Publishing LLC.show moreshow less

Export metadata

Additional Services

Share in Twitter Search Google Scholar Statistics
Metadaten
Author: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, Yoshihisa Harada, Michael J. Bogan, Philippe Wernet, Alexander FöhlischORCiDGND, Lars G. M. Pettersson, Anders Nilsson
DOI:https://doi.org/10.1063/1.4905603
ISSN:0021-9606 (print)
ISSN:1089-7690 (online)
Pubmed Id:http://www.ncbi.nlm.nih.gov/pubmed?term=25637993
Parent Title (English):The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr
Publisher:American Institute of Physics
Place of publication:Melville
Document Type:Article
Language:English
Year of first Publication:2015
Year of Completion:2015
Release Date:2017/03/27
Volume:142
Issue:4
Pagenumber:9
Funder:National Science Foundation (US) [CHE-0809324]; Department of Energy through the SLAC Laboratory Directed Research and Development Program, Office of Basic Energy Sciences (BES) through SSRL; Department of Energy through the SLAC Laboratory Directed Research and Development Program, Office of Basic Energy Sciences (BES) through LCLS; AMOS program within the Chemical Sciences, Geosciences, and Biosciences Division of the Office of BES; Swedish Research Council, Lennanders Stiftelse; Volkswagen Stiftung; Helmholtz Virtual Institute Dynamic Pathways in Multidimensional Landscapes; LCLS, Stanford University through the Stanford Institute for Materials Energy Sciences (SIMES); Lawrence Berkeley National Laboratory (LBNL); University of Hamburg through the BMBF priority program [FSP 301]; Center for Free Electron Laser Science (CFEL)
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Physik und Astronomie
Peer Review:Referiert