TY  - JOUR
A1  - Sellberg, Jonas A.
A1  - McQueen, Trevor A.
A1  - Laksmono, Hartawan
A1  - Schreck, Simon
A1  - Beye, Martin
A1  - DePonte, Daniel P.
A1  - Kennedy, Brian
A1  - Nordlund, Dennis
A1  - Sierra, Raymond G.
A1  - Schlesinger, Daniel
A1  - Tokushima, Takashi
A1  - Zhovtobriukh, Iurii
A1  - Eckert, Sebastian
A1  - Segtnan, Vegard H.
A1  - Ogasawara, Hirohito
A1  - Kubicek, Katharina
A1  - Techert, Simone
A1  - Bergmann, Uwe
A1  - Dakovski, Georgi L.
A1  - Schlotter, William F.
A1  - Harada, Yoshihisa
A1  - Bogan, Michael J.
A1  - Wernet, Philippe
A1  - Föhlisch, Alexander
A1  - Pettersson, Lars G. M.
A1  - Nilsson, Anders
T1  - X-ray emission spectroscopy of bulk liquid water in "no-man's land"
JF  - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr
N2  - 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. (C) 2015 AIP Publishing LLC.
Y1  - 2015
U6  - https://doi.org/10.1063/1.4905603
SN  - 0021-9606
SN  - 1089-7690
VL  - 142
IS  - 4
PB  - American Institute of Physics
CY  - Melville
ER  -