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Structure and Dynamics of Single-Crystalline Ice Ih Interfaces

Research Project

Project/Area Number 18H01934
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 32010:Fundamental physical chemistry-related
Research InstitutionSaitama University

Principal Investigator

Yamaguchi Shoichi  埼玉大学, 理工学研究科, 教授 (60250239)

Co-Investigator(Kenkyū-buntansha) 野嶋 優妃  埼玉大学, 理工学研究科, 助教 (90756404)
Project Period (FY) 2018-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥17,160,000 (Direct Cost: ¥13,200,000、Indirect Cost: ¥3,960,000)
Fiscal Year 2021: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2020: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2019: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2018: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Keywords氷 / 分光 / 表面 / 界面 / 非線形 / 和周波 / 振動分光 / 和周波発生分光 / ヘテロダイン検出 / プロトン秩序 / 水 / 和周波発生 / 水素結合 / 氷Ih / 水素の位置の無秩序性 / 残余エントロピー / OH伸縮振動 / 振動スペクトル / 表面緩和 / 水分子の上下の配向 / ice rule / proton disorder / ヘテロダイン検出和周波発生 / 同位体希釈 / 単結晶氷Ih
Outline of Final Research Achievements

Among numerous crystalline phases of ice, the Ih phase is the most stable above 72 K at atmospheric pressure. It is well established that the orientations of water molecules in the bulk of ice Ih are statistical without long-range order. However, the orientational order of water at the surface of ice Ih has been enigmatic. Here we show that the surface of ice Ih at 100 K has hydrogen order with the OH group pointing upward to the air ("H-up" orientation). We applied nonlinear optical spectroscopy and theoretical modeling to the surface of isotopically pure and diluted ice Ih and observed OH stretch vibrational signatures attributed to H-up ordering. Furthermore, we found that this hydrogen order takes place despite more inhomogeneous microenvironment at the surface than in the bulk. Our results suggest the prominent role of the surface to allow the reorientation of water molecules for hydrogen ordering that is virtually prohibited in the bulk.

Academic Significance and Societal Importance of the Research Achievements

今回の研究で,氷Ihの表面はH-upの水素秩序構造を有することが分かったが,なぜそのような秩序が発生するのかは明らかでない.72 K以下のバルクでは,水素無秩序構造の氷Ihよりも水素秩序構造の氷XIの方が安定であることが知られているが,IhからXIへの相転移は欠陥の導入なしでは速度論的に不可能である.表面では水素結合ネットワークが切断され,水分子の並進と回転運動の自由度がバルクよりも大きく,フラストレーションがより小さい.それによって表面では水素秩序構造への“相転移”が速度論的に可能となっているのかもしれない.表面での秩序-無秩序転移の機構解明には,温度依存性の研究が将来的に重要になる.

Report

(5 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Annual Research Report
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • Research Products

    (7 results)

All 2022 2020 2019 2018

All Journal Article (6 results) (of which Peer Reviewed: 6 results) Presentation (1 results) (of which Int'l Joint Research: 1 results,  Invited: 1 results)

  • [Journal Article] Raman spectroscopy of isotopically pure and diluted high‐ and low‐density amorphous ices2022

    • Author(s)
      Ishihara Senri、Takayama Tetsuyuki、Sakaguchi Miyuki、Otosu Takuhiro、Yagasaki Takuma、Suzuki Yoshiharu、Yamaguchi Shoichi
    • Journal Title

      Journal of Raman Spectroscopy

      Volume: - Issue: 10 Pages: 1773-1784

    • DOI

      10.1002/jrs.6322

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Resolving the Controversy over Dipole versus Quadrupole Mechanism of Bend Vibration of Water in Vibrational Sum Frequency Generation Spectra2020

    • Author(s)
      M. Ahmed、S. Nihonyanagi、A. Kundu、S. Yamaguchi、T. Tahara
    • Journal Title

      The Journal of Physical Chemistry Letters

      Volume: 11 Issue: 21 Pages: 9123-9130

    • DOI

      10.1021/acs.jpclett.0c02644

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Structure of water and polymer at the buried polymer/water interface unveiled using heterodyne-detected vibrational sum frequency generation2020

    • Author(s)
      A. Myalitsin、S. Ghosh、S. Urashima、S. Nihonyanagi、S. Yamaguchi、T. Aoki、T. Tahara
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 22 Issue: 29 Pages: 16527-16531

    • DOI

      10.1039/d0cp02618b

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Comment on “Phase-sensitive sum frequency vibrational spectroscopic study of air/water interfaces: H2O, D2O, and diluted isotopic mixtures” [J. Chem. Phys. 150, 144701 (2019)]2020

    • Author(s)
      M. Ahmed、Y. Nojima、S. Nihonyanagi、S. Yamaguchi、T. Tahara
    • Journal Title

      The Journal of Chemical Physics

      Volume: 152 Issue: 23 Pages: 237101-237101

    • DOI

      10.1063/1.5126062

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Hydrogen order at the surface of ice Ih revealed by vibrational spectroscopy2020

    • Author(s)
      Yuki Nojima, Yuki Shioya, Hajime Torii, Shoichi Yamaguchi
    • Journal Title

      Chemical Communications

      Volume: 56 Issue: 33 Pages: 4663-4666

    • DOI

      10.1039/d0cc00865f

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Perspective on sum frequency generation spectroscopy of ice surfaces and interfaces2019

    • Author(s)
      Yamaguchi Shoichi、Suzuki Yudai、Nojima Yuki、Otosu Takuhiro
    • Journal Title

      Chemical Physics

      Volume: 522 Pages: 199-210

    • DOI

      10.1016/j.chemphys.2019.03.005

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Presentation] Vibrational Coupling at Water and Ice Surfaces2018

    • Author(s)
      Shoichi Yamaguchi
    • Organizer
      Telluride workshop "Nonlinear Optics at Interfaces",
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited

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Published: 2018-04-23   Modified: 2023-01-30  

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