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Is the structure of hydroxide dihydrate OH−(H2O)2? An ab initio path integral molecular dynamics study

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Abstract

We carried out ab initio path integral molecular dynamics simulations at room temperature for OH−(H2O) n (n = 1, 2) clusters to elucidate the ionic hydrogen bond structure with full thermal and nuclear quantum effects. We found that the hydrogen-bonded proton is located near the water molecule in the case of n = 2, while the proton is located at the center between hydroxide ion and the water molecule in the case of n = 1. Thus, the solvated hydroxide structure \({\text{HO}}{-}{\text{H}} \cdots{\text{OH}}\) is found in n = 2, while the proton sharing hydroxide structure \({\text{HO}} \cdots {\text{H}} \cdots {\text{OH}}\) is in n = 1. We found that the nature of hydrogen bonds significantly changes with the number of water molecules around the hydroxide. We also compared these results with those of F−(H2O) n (n = 1, 2) clusters.

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Acknowledgments

Financial support was provided by Grant-in-Aid for Scientific Research and for the priority area by Ministry of Education, Culture, Sports, Science, and Technology, Japan for YK and MT. KT thanks Academia Sinica, National Center for High Performance Computing of Taiwan and Ministry of Science and Technology (NSC100-2113-M-001-004-MY2, NSC 102-2113-M-001-012-MY3) of Taiwan for support.

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Authors and Affiliations

  1. Graduate School of Nanobioscience, Yokohama City University, Yokohama, 236-0027, Japan

    Yudai Ogata & Masanori Tachikawa

  2. RIKEN Advanced Institute for Computational Science, Kobe, 650-0047, Japan

    Yukio Kawashima

  3. Institute of Atomic and Molecular Sciences, Academia Sinica, P.O. Box 23-166, Taipei, 10617, Taiwan, ROC

    Kaito Takahashi

Authors
  1. Yudai Ogata
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  2. Yukio Kawashima
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  3. Kaito Takahashi
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  4. Masanori Tachikawa
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Correspondence to Masanori Tachikawa.

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Published as part of the special collection of articles derived from the 9th Congress on Electronic Structure: Principles and Applications (ESPA 2014).

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Ogata, Y., Kawashima, Y., Takahashi, K. et al. Is the structure of hydroxide dihydrate OH−(H2O)2? An ab initio path integral molecular dynamics study. Theor Chem Acc 134, 1587 (2015). https://doi.org/10.1007/s00214-014-1587-1

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  • DOI: https://doi.org/10.1007/s00214-014-1587-1

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