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Title: Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures

Abstract

Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here in this paper, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factor reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10–100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]
  1. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences and Computational Sciences and Engineering Division
  4. {Larry} M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1436948
Alternate Identifier(s):
OSTI ID: 1436541
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Letters
Additional Journal Information:
Journal Volume: 120; Journal Issue: 19; Journal ID: ISSN 0031-9007
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Prisk, Timothy, Hoffmann, Christina, Kolesnikov, Alexander I., Mamontov, Eugene, Podlesnyak, Andrey A., Wang, Xiaoping, Kent, Paul R., and Anovitz, Lawrence. Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures. United States: N. p., 2018. Web. doi:10.1103/PhysRevLett.120.196001.
Prisk, Timothy, Hoffmann, Christina, Kolesnikov, Alexander I., Mamontov, Eugene, Podlesnyak, Andrey A., Wang, Xiaoping, Kent, Paul R., & Anovitz, Lawrence. Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures. United States. doi:10.1103/PhysRevLett.120.196001.
Prisk, Timothy, Hoffmann, Christina, Kolesnikov, Alexander I., Mamontov, Eugene, Podlesnyak, Andrey A., Wang, Xiaoping, Kent, Paul R., and Anovitz, Lawrence. Wed . "Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures". United States. doi:10.1103/PhysRevLett.120.196001. https://www.osti.gov/servlets/purl/1436948.
@article{osti_1436948,
title = {Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures},
author = {Prisk, Timothy and Hoffmann, Christina and Kolesnikov, Alexander I. and Mamontov, Eugene and Podlesnyak, Andrey A. and Wang, Xiaoping and Kent, Paul R. and Anovitz, Lawrence},
abstractNote = {Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here in this paper, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factor reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10–100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.},
doi = {10.1103/PhysRevLett.120.196001},
journal = {Physical Review Letters},
number = 19,
volume = 120,
place = {United States},
year = {2018},
month = {5}
}

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Cited by: 2 works
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Figures / Tables:

FIG. 1 FIG. 1: The crystal structure of hemimorphite viewed along the b axis. The framework is shown as a traditional ball-and-stick model with anisotropic displacement parameters at 65% probability. The hydroxyl proton and the water molecule are shown as nuclear density isosurfaces. Panel (a) illustratesmodelAfor phase I, and panel (b) illustratesmore » the unit cell for phase II.ModelBfor phase I is the same as shown on panel (b) with randomoccupancy of thewatermolecules. Figure designations:Nuclear density isosurfaces forwater oxygens (red), nuclear density isosurfaces for water or hydroxyl protons (green), SiO4 tetrahedra (blue), ZnO3(OH) tetrahedra (gray), framework oxygen (red).« less

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