skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

This content will become publicly available on May 28, 2020

Title: Effect of fine-tuning pore structures on the dynamics of confined water

Abstract

Confinement of water in sub-nanometer pores strongly alters its vibrational dynamics from that of bulk water. The effect of confinement can, furthermore, be finely tuned by small changes in the size and symmetry of the confining pore. Using inelastic neutron scattering (INS), we recently studied the dynamics of water confined in the channels of beryl and cordierite in which, at low temperatures, water shows similar intramolecular mode behavior, very soft intermolecular librational and translational bands, and neutron-recoil scattering at large momentum and energy transfer perpendicular to the channels. All these features indicate an absence of hydrogen bonds acting on the water molecule at low temperature and a shallow water potential. In addition, we observed multiple tunneling modes (between 0.66 and 14.7 meV) in the INS spectra of beryl, due to transitions between the split ground-state of the water protons. Int his study, we present a study of: (i) the effect of pressure on the dynamics of water in beryl, (ii) the dynamics of water in beryl containing alkali metals (which results in changing the orientation of the water molecule in the crystal), and (iii) the dynamics of water in cordierite at low energies. We found a shift in the tunnelingmore » and vibrational modes of water in beryl to higher energies at 22 kbar relative to 1 bar. No tunneling modes were observed for water in cordierite and type-II water in beryl. Therefore, we conclude that very small differences in the size and structure of the pores and the orientation of the water molecule in these minerals result in changes in the potential of the water protons and drastic changes in the confined water dynamics.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [4]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
  3. Univ. of Manitoba, Winnipeg, Manitoba (Canada). Dept. of Geological Sciences
  4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division; Natural Sciences and Engineering Research Council of Canada (NSERC)
OSTI Identifier:
1545022
Alternate Identifier(s):
OSTI ID: 1518527; OSTI ID: 1523736
Report Number(s):
[PNNL-SA-142207]
[Journal ID: ISSN 0021-9606]
Grant/Contract Number:  
[AC05-76RL01830; AC05-00OR22725]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
[ Journal Volume: 150; Journal Issue: 20]; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kolesnikov, A. I., Anovitz, L. M., Hawthorne, F. C., Podlesnyak, A., and Schenter, G. K. Effect of fine-tuning pore structures on the dynamics of confined water. United States: N. p., 2019. Web. doi:10.1063/1.5096771.
Kolesnikov, A. I., Anovitz, L. M., Hawthorne, F. C., Podlesnyak, A., & Schenter, G. K. Effect of fine-tuning pore structures on the dynamics of confined water. United States. doi:10.1063/1.5096771.
Kolesnikov, A. I., Anovitz, L. M., Hawthorne, F. C., Podlesnyak, A., and Schenter, G. K. Tue . "Effect of fine-tuning pore structures on the dynamics of confined water". United States. doi:10.1063/1.5096771.
@article{osti_1545022,
title = {Effect of fine-tuning pore structures on the dynamics of confined water},
author = {Kolesnikov, A. I. and Anovitz, L. M. and Hawthorne, F. C. and Podlesnyak, A. and Schenter, G. K.},
abstractNote = {Confinement of water in sub-nanometer pores strongly alters its vibrational dynamics from that of bulk water. The effect of confinement can, furthermore, be finely tuned by small changes in the size and symmetry of the confining pore. Using inelastic neutron scattering (INS), we recently studied the dynamics of water confined in the channels of beryl and cordierite in which, at low temperatures, water shows similar intramolecular mode behavior, very soft intermolecular librational and translational bands, and neutron-recoil scattering at large momentum and energy transfer perpendicular to the channels. All these features indicate an absence of hydrogen bonds acting on the water molecule at low temperature and a shallow water potential. In addition, we observed multiple tunneling modes (between 0.66 and 14.7 meV) in the INS spectra of beryl, due to transitions between the split ground-state of the water protons. Int his study, we present a study of: (i) the effect of pressure on the dynamics of water in beryl, (ii) the dynamics of water in beryl containing alkali metals (which results in changing the orientation of the water molecule in the crystal), and (iii) the dynamics of water in cordierite at low energies. We found a shift in the tunneling and vibrational modes of water in beryl to higher energies at 22 kbar relative to 1 bar. No tunneling modes were observed for water in cordierite and type-II water in beryl. Therefore, we conclude that very small differences in the size and structure of the pores and the orientation of the water molecule in these minerals result in changes in the potential of the water protons and drastic changes in the confined water dynamics.},
doi = {10.1063/1.5096771},
journal = {Journal of Chemical Physics},
number = [20],
volume = [150],
place = {United States},
year = {2019},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on May 28, 2020
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Vibrational states of a water molecule in a nano-cavity of beryl crystal lattice
journal, June 2014

  • Zhukova, Elena S.; Torgashev, Victor I.; Gorshunov, Boris P.
  • The Journal of Chemical Physics, Vol. 140, Issue 22
  • DOI: 10.1063/1.4882062

Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases
journal, September 2007

  • VandeVondele, Joost; Hutter, Jürg
  • The Journal of Chemical Physics, Vol. 127, Issue 11
  • DOI: 10.1063/1.2770708

Mantid—Data analysis and visualization package for neutron scattering and μ SR experiments
journal, November 2014

  • Arnold, O.; Bilheux, J. C.; Borreguero, J. M.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 764
  • DOI: 10.1016/j.nima.2014.07.029

DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data
journal, November 2009

  • Azuah, Richard Tumanjong; Kneller, Larry R.; Qiu, Yiming
  • Journal of Research of the National Institute of Standards and Technology, Vol. 114, Issue 6
  • DOI: 10.6028/jres.114.025

Low temperature dynamics of molecular H2O in bassanite, gypsum and cordierite investigated by high resolution incoherent inelastic neutron scattering
journal, December 1994

  • Winkler, Bj�rn; Hennion, Bernard
  • Physics and Chemistry of Minerals, Vol. 21, Issue 8
  • DOI: 10.1007/bf00203929

Clamp cell with in situ pressure monitoring for low-temperature neutron scattering measurements
journal, August 2018


Anomalously soft dynamics of water in carbon nanotubes
journal, November 2006


Solid solutions of (Mg, Fe2+)-cordierite: Synthesis, water content, and magnetic properties
journal, April 2011


Inelastic and deep inelastic neutron spectroscopy of water molecules under ultra-confinement
journal, July 2018


SEQUOIA: A Newly Operating Chopper Spectrometer at the SNS
journal, November 2010


A comparison of four direct geometry time-of-flight spectrometers at the Spallation Neutron Source
journal, April 2014

  • Stone, M. B.; Niedziela, J. L.; Abernathy, D. L.
  • Review of Scientific Instruments, Vol. 85, Issue 4
  • DOI: 10.1063/1.4870050

Ar, N2, and CO2 in the structural cavities of cordierite, an optical and X-ray single-crystal study
journal, September 1985

  • Armbruster, Thomas
  • Physics and Chemistry of Minerals, Vol. 12, Issue 4
  • DOI: 10.1007/bf00311293

THz–IR spectroscopy of single H 2 O molecules confined in nanocage of beryl crystal lattice
journal, October 2014


Strong Anisotropic Dynamics of Ultra-Confined Water
journal, August 2014

  • Kolesnikov, Alexander I.; Anovitz, Lawrence M.; Mamontov, Eugene
  • The Journal of Physical Chemistry B, Vol. 118, Issue 47
  • DOI: 10.1021/jp505355b

Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach
journal, April 2005

  • VandeVondele, Joost; Krack, Matthias; Mohamed, Fawzi
  • Computer Physics Communications, Vol. 167, Issue 2
  • DOI: 10.1016/j.cpc.2004.12.014

Neutron scattering lengths and cross sections
journal, January 1992


Quantum rotation of ortho and para-water encapsulated in a fullerene cage
journal, July 2012

  • Beduz, C.; Carravetta, M.; Chen, J. Y. - C.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 32
  • DOI: 10.1073/pnas.1210790109

The real topological configuration of the extra-framework content in alkali-poor beryl: A multi-methodological study
journal, January 2006

  • Gatta, G. Diego; Nestola, F.; Bromiley, G. D.
  • American Mineralogist, Vol. 91, Issue 1
  • DOI: 10.2138/am.2006.1896

Compressibility and equation of state of beryl (Be3Al2Si6O18) by using a diamond anvil cell and in situ synchrotron X-ray diffraction
journal, March 2015


The new cold neutron chopper spectrometer at the Spallation Neutron Source: Design and performance
journal, August 2011

  • Ehlers, G.; Podlesnyak, A. A.; Niedziela, J. L.
  • Review of Scientific Instruments, Vol. 82, Issue 8
  • DOI: 10.1063/1.3626935

The cold neutron chopper spectrometer at the Spallation Neutron Source—A review of the first 8 years of operation
journal, September 2016

  • Ehlers, G.; Podlesnyak, A. A.; Kolesnikov, A. I.
  • Review of Scientific Instruments, Vol. 87, Issue 9
  • DOI: 10.1063/1.4962024

Quantum Behavior of Water Molecules Confined to Nanocavities in Gemstones
journal, June 2013

  • Gorshunov, Boris P.; Zhukova, Elena S.; Torgashev, Victor I.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 12
  • DOI: 10.1021/jz400782j

Separable dual-space Gaussian pseudopotentials
journal, July 1996