TY - JOUR
T1 - Unveiling subsurface hydrogen-bond structure of hexagonal water ice
AU - Otsuki, Yuji
AU - Sugimoto, Toshiki
AU - Ishiyama, Tatsuya
AU - Morita, Akihiro
AU - Watanabe, Kazuya
AU - Matsumoto, Yoshiyasu
N1 - Funding Information:
We are grateful to N. Aiga, K. Harada, F. Kato, T. Hama, and H. Kato for fruitful discussions. This work was supported by MEXT KAKENHI: Grant-in-Aid for Scientific Research on Innovative Areas, Nos. 16H00937 and 25104003; JSPS KAKENHI Grant-in-Aid for Young Scientists (A), No. 16H06029; Grant-in-Aid for Scientific Research (A), No. 16H02249; Grants-in-Aid for Scientific Research (B) No. 16H04095; Grant-in-Aid for JSPS Research Fellow No. 17J08352. The computations were performed using Supercomputer Center of the Institute for Solid State Physics, the University of Tokyo, and Research Center for Computational Science, Okazaki, Japan.
Publisher Copyright:
© 2017 American Physical Society.
PY - 2017/9/5
Y1 - 2017/9/5
N2 - The phase-resolved sum-frequency-generation (SFG) spectrum for the basal face of hexagonal ice is reported and is interpreted by molecular dynamics simulations combined with ab initio quantum calculations. Here, we demonstrate that the line shape of the SFG spectra of isotope-diluted OH chromophores is a sensitive indicator of structural rumpling uniquely emerging at the subsurface of hexagonal ice. In the outermost subsurface between the first (B1) and second (B2) bilayer, the hydrogen bond of OB1-H"OB2 is weaker than that of OB1"H-OB2. This implies that subsurface O-O distance is laterally altered, depending on the direction of O-H bond along the surface normal: H-up or H-down, which is in stark contrast to bulk hydrogen bonds. This new finding uncovers how water molecules undercoordinated at the topmost surface influence on the subsurface structural rumpling associated with orientational frustration inherent in water ice.
AB - The phase-resolved sum-frequency-generation (SFG) spectrum for the basal face of hexagonal ice is reported and is interpreted by molecular dynamics simulations combined with ab initio quantum calculations. Here, we demonstrate that the line shape of the SFG spectra of isotope-diluted OH chromophores is a sensitive indicator of structural rumpling uniquely emerging at the subsurface of hexagonal ice. In the outermost subsurface between the first (B1) and second (B2) bilayer, the hydrogen bond of OB1-H"OB2 is weaker than that of OB1"H-OB2. This implies that subsurface O-O distance is laterally altered, depending on the direction of O-H bond along the surface normal: H-up or H-down, which is in stark contrast to bulk hydrogen bonds. This new finding uncovers how water molecules undercoordinated at the topmost surface influence on the subsurface structural rumpling associated with orientational frustration inherent in water ice.
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U2 - 10.1103/PhysRevB.96.115405
DO - 10.1103/PhysRevB.96.115405
M3 - Article
AN - SCOPUS:85030147866
SN - 2469-9950
VL - 96
JO - Physical Review B
JF - Physical Review B
IS - 11
M1 - 115405
ER -