Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Anomalously large isotope effect in the glass transition of water

Abstract

Here we present the discovery of an unusually large isotope effect in the structural relaxation and the glass transition temperature Tg of water. Dielectric relaxation spectroscopy of low-density as well as of vapor deposited amorphous water reveal Tg differences of 10±2K between H2O and D2O, sharply contrasting with other hydrogen bonded liquids for which H/D exchange increases Tg by typically less than 1K. We show that the large isotope effect and the unusual variation of relaxation times in water at low temperatures can be explained in terms of quantum effects. Thus, our findings shed new light on water's peculiar low-temperature dynamics and the possible role of quantum effects in its structural relaxation, and possibly in dynamics of other low molecular weight liquids.

Authors:
 [1];  [2];  [3];  [3];  [1];  [1];  [4];  [2];  [5];  [1];  [3];  [2]
+ Show Author Affiliations
  1. Dortmund Univ. of Technology (Germany). Dept. of Physics
  2. Univ. of Tennessee, Knoxville, TN (United States). Joint Inst. for Neutron Sciences, Dept. of Chemistry; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Science Division
  3. Univ. of Innsbruck, Innsbruck (Austria). Inst. of Physical Chemistry
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division
  5. Arizona State Univ., Tempe, AZ (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1286807
Grant/Contract Number:  
AC05-00OR22725; CHE-1213444; CHE-1026124; BO1301
Resource Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 111; Journal Issue: 49; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; dynamics of water; isotope effect; quantum effects; glass transition; amorphous ice

Citation Formats

Gainaru, Catalin, Agapov, Alexander L., Fuentes-Landete, Violeta, Amann-Winkel, Katrin, Nelson, Helge, Köster, Karsten W., Kolesnikov, Alexander I., Novikov, Vladimir N., Richert, Ranko, Böhmer, Roland, Loerting, Thomas, and Sokolov, Alexei P. Anomalously large isotope effect in the glass transition of water. United States: N. p., 2014. Web. doi:10.1073/pnas.1411620111.
Copy to clipboard
Gainaru, Catalin, Agapov, Alexander L., Fuentes-Landete, Violeta, Amann-Winkel, Katrin, Nelson, Helge, Köster, Karsten W., Kolesnikov, Alexander I., Novikov, Vladimir N., Richert, Ranko, Böhmer, Roland, Loerting, Thomas, & Sokolov, Alexei P. Anomalously large isotope effect in the glass transition of water. United States. https://doi.org/10.1073/pnas.1411620111
Copy to clipboard
Gainaru, Catalin, Agapov, Alexander L., Fuentes-Landete, Violeta, Amann-Winkel, Katrin, Nelson, Helge, Köster, Karsten W., Kolesnikov, Alexander I., Novikov, Vladimir N., Richert, Ranko, Böhmer, Roland, Loerting, Thomas, and Sokolov, Alexei P. Mon . "Anomalously large isotope effect in the glass transition of water". United States. https://doi.org/10.1073/pnas.1411620111. https://www.osti.gov/servlets/purl/1286807.
Copy to clipboard
@article{osti_1286807,
title = {Anomalously large isotope effect in the glass transition of water},
author = {Gainaru, Catalin and Agapov, Alexander L. and Fuentes-Landete, Violeta and Amann-Winkel, Katrin and Nelson, Helge and Köster, Karsten W. and Kolesnikov, Alexander I. and Novikov, Vladimir N. and Richert, Ranko and Böhmer, Roland and Loerting, Thomas and Sokolov, Alexei P.},
abstractNote = {Here we present the discovery of an unusually large isotope effect in the structural relaxation and the glass transition temperature Tg of water. Dielectric relaxation spectroscopy of low-density as well as of vapor deposited amorphous water reveal Tg differences of 10±2K between H2O and D2O, sharply contrasting with other hydrogen bonded liquids for which H/D exchange increases Tg by typically less than 1K. We show that the large isotope effect and the unusual variation of relaxation times in water at low temperatures can be explained in terms of quantum effects. Thus, our findings shed new light on water's peculiar low-temperature dynamics and the possible role of quantum effects in its structural relaxation, and possibly in dynamics of other low molecular weight liquids.},
doi = {10.1073/pnas.1411620111},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 49,
volume = 111,
place = {United States},
year = {Mon Nov 24 00:00:00 EST 2014},
month = {Mon Nov 24 00:00:00 EST 2014}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1073/pnas.1411620111
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 52 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Two-channel impedance spectroscopy for the simultaneous measurement of two samples
journal, March 2012

  • Singh, Lokendra P.; Richert, Ranko
  • Review of Scientific Instruments, Vol. 83, Issue 3
  • DOI: 10.1063/1.3697732

Dielectric relaxation of H2O/D2O mixtures
journal, February 1993

Universal scaling between structural relaxation and vibrational dynamics in glass-forming liquids and polymers
journal, December 2007

  • Larini, L.; Ottochian, A.; De Michele, C.
  • Nature Physics, Vol. 4, Issue 1
  • DOI: 10.1038/nphys788

Thermodynamic determination of fragility in liquids and a fragile-to-strong liquid transition in water
journal, April 1999

  • Ito, Kaori; Moynihan, Cornelius T.; Angell, C. Austen
  • Nature, Vol. 398, Issue 6727
  • DOI: 10.1038/19042

Structural Relaxation Dynamics in Binary Glass-Forming Molecular Liquids with Ideal and Complex Mixing Behavior
journal, March 2010

  • Wang, Li-Min; Tian, Yongjun; Liu, Riping
  • The Journal of Physical Chemistry B, Vol. 114, Issue 10
  • DOI: 10.1021/jp912223j

Inelastic neutron scattering studies of hydrogen bonding in ices
journal, October 1996

  • Li, Jichen
  • The Journal of Chemical Physics, Vol. 105, Issue 16
  • DOI: 10.1063/1.472525

Neutron spectroscopic investigation of dynamics of water ice
journal, June 2002

Preparation of Amorphous Solid Water
journal, January 1972

  • Olander, D. S.; Rice, S. A.
  • Proceedings of the National Academy of Sciences, Vol. 69, Issue 1
  • DOI: 10.1073/pnas.69.1.98

Low-temperature specific heat of structural and orientational glasses of simple alcohols
journal, March 2003

  • Ramos, M. A.; Tal n., C.; Jim nez-Riob o., R. J.
  • Journal of Physics: Condensed Matter, Vol. 15, Issue 11
  • DOI: 10.1088/0953-8984/15/11/323

Dielectric relaxation of water and heavy water in the whole fluid phase
journal, February 1999

  • Okada, K.; Yao, M.; Hiejima, Y.
  • The Journal of Chemical Physics, Vol. 110, Issue 6
  • DOI: 10.1063/1.477897

Anomalous Proton Dynamics in Ice at Low Temperatures
journal, October 2009

Amorphous Water
journal, June 2004

Reversibility and isotope effect of the calorimetric glass → liquid transition of low-density amorphous ice
journal, January 2010

  • Elsaesser, Michael S.; Winkel, Katrin; Mayer, Erwin
  • Phys. Chem. Chem. Phys., Vol. 12, Issue 3
  • DOI: 10.1039/b917662d

Multiphonon contributions in inelastic neutron scattering spectra of ice
journal, June 1997

Supercooled and glassy water
journal, October 2003

Nuclear Quantum Effects in Water
journal, July 2008

Nonexponential relaxations in strong and fragile glass formers
journal, September 1993

  • Böhmer, R.; Ngai, K. L.; Angell, C. A.
  • The Journal of Chemical Physics, Vol. 99, Issue 5
  • DOI: 10.1063/1.466117

Isotope effects in water as investigated by neutron diffraction and path integral molecular dynamics
journal, June 2012

Water's second glass transition
journal, October 2013

  • Amann-Winkel, K.; Gainaru, C.; Handle, P. H.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 44
  • DOI: 10.1073/pnas.1311718110

The local and intermediate range structures of the five amorphous ices at 80K and ambient pressure: A Faber-Ziman and Bhatia-Thornton analysis
journal, November 2006

  • Bowron, D. T.; Finney, J. L.; Hallbrucker, A.
  • The Journal of Chemical Physics, Vol. 125, Issue 19
  • DOI: 10.1063/1.2378921

Isotope effects in liquid water probed by x-ray Raman spectroscopy
journal, July 2007

Study of the low‐temperature ’’transition’’ in ice Ih by thermally stimulated depolarization measurements
journal, May 1975

  • Johari, G. P.; Jones, S. J.
  • The Journal of Chemical Physics, Vol. 62, Issue 10
  • DOI: 10.1063/1.430303

Direct determination of kinetic fragility indices of glassforming liquids by differential scanning calorimetry: Kinetic versus thermodynamic fragilities
journal, December 2002

  • Wang, Li-Min; Velikov, V.; Angell, C. A.
  • The Journal of Chemical Physics, Vol. 117, Issue 22
  • DOI: 10.1063/1.1517607

Rotational dynamics in supercooled water from nuclear spin relaxation and molecular simulations
journal, May 2012

  • Qvist, Johan; Mattea, Carlos; Sunde, Erik P.
  • The Journal of Chemical Physics, Vol. 136, Issue 20
  • DOI: 10.1063/1.4720941

Design considerations in the use of interdigitated microsensor electrode arrays (IMEs) for impedimetric characterization of biomimetic hydrogels
journal, November 2010

  • Yang, Liju; Guiseppi-Wilson, Adilah; Guiseppi-Elie, Anthony
  • Biomedical Microdevices, Vol. 13, Issue 2
  • DOI: 10.1007/s10544-010-9492-4

Insights into Phases of Liquid Water from Study of Its Unusual Glass-Forming Properties
journal, February 2008

Water II is a "strong" liquid
journal, June 1993

Temperature dependence of dielectric relaxation in H 2 O and D 2 O ice. A dissipative quantum tunneling approach
journal, July 1993

  • Bruni, Fabio; Consolini, Giuseppe; Careri, Giorgio
  • The Journal of Chemical Physics, Vol. 99, Issue 1
  • DOI: 10.1063/1.465778

Isotope effect on the glass transition and crystallization of hyperquenched glassy water
journal, June 1990

  • Johari, G. P.; Hallbrucker, Andreas; Mayer, Erwin
  • The Journal of Chemical Physics, Vol. 92, Issue 11
  • DOI: 10.1063/1.458593

Quantum Tunneling in Complex Systems: The Semiclassical Approach
book, January 2007

The relationship between liquid, supercooled and glassy water
journal, November 1998

  • Mishima, Osamu; Stanley, H. Eugene
  • Nature, Vol. 396, Issue 6709
  • DOI: 10.1038/24540

The Pressure Dependence of Self Diffusion in Supercooled Light and Heavy Water
journal, October 1988

  • Prielmeier, F. X.; Lang, E. W.; Speedy, R. J.
  • Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 92, Issue 10
  • DOI: 10.1002/bbpc.198800282

Neutron Scattering Studies of Vapor Deposited Amorphous Ice
journal, September 1997

Theoretical and Experimental Considerations on the Enthalpic Relaxation of Organic Glasses using Differential Scanning Calorimetry
journal, January 2010

  • Mao, Chen; Chamarthy, Sai Prasanth; Byrn, Stephen R.
  • The Journal of Physical Chemistry B, Vol. 114, Issue 1
  • DOI: 10.1021/jp906633k

Unraveling quantum mechanical effects in water using isotopic fractionation
journal, May 2012

  • Markland, T. E.; Berne, B. J.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 21
  • DOI: 10.1073/pnas.1203365109

The dielectric relaxation time of ice V, its partial anti-ferroelectric ordering and the role of Bjerrum defects
journal, August 2001

  • Johari, G. P.; Whalley, E.
  • The Journal of Chemical Physics, Vol. 115, Issue 7
  • DOI: 10.1063/1.1386903

Isotope quantum effects in water around the freezing point
journal, April 2006

  • Hart, R. T.; Mei, Q.; Benmore, C. J.
  • The Journal of Chemical Physics, Vol. 124, Issue 13
  • DOI: 10.1063/1.2181974

Quantum fluctuations can promote or inhibit glass formation
journal, January 2011

  • Markland, Thomas E.; Morrone, Joseph A.; Berne, Bruce J.
  • Nature Physics, Vol. 7, Issue 2
  • DOI: 10.1038/nphys1865

Infrared and vapor flux studies of vapor-deposited amorphous and crystalline water ice films between 90 and 145 K
journal, December 2001

  • La Spisa, Sabrina; Waldheim, Matthew; Lintemoot, Jaime
  • Journal of Geophysical Research: Planets, Vol. 106, Issue E12
  • DOI: 10.1029/2000JE001305

Role of Quantum Effects in the Glass Transition
journal, February 2013

Deuteration effects in the thermal conductivity of molecular glasses
journal, June 2011

  • Krivchikov, A. I.; Bermejo, F. J.; Sharapova, I. V.
  • Low Temperature Physics, Vol. 37, Issue 6
  • DOI: 10.1063/1.3622630

The existence of supercooled liquid water at 150?K
journal, April 1999

  • Smith, R. Scott; Kay, Bruce D.
  • Nature, Vol. 398, Issue 6730
  • DOI: 10.1038/19725

The Dielectric Properties of Water and Heavy Water
journal, February 1948

  • Collie, C. H.; Hasted, J. B.; Ritson, D. M.
  • Proceedings of the Physical Society, Vol. 60, Issue 2
  • DOI: 10.1088/0959-5309/60/2/304
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Diffusive dynamics during the high-to-low density transition in amorphous ice
    text, January 2017

    • Perakis, Fivos; Amann-Winkel, Katrin; Lehmkühler, Felix
    • Deutsches Elektronen-Synchrotron, DESY, Hamburg
    • DOI: 10.3204/pubdb-2017-08683

    Thermodynamic and kinetic isotope effects on the order–disorder transition of ice XIV to ice XII
    journal, January 2018

    • Fuentes-Landete, Violeta; Köster, Karsten W.; Böhmer, Roland
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 33
    • DOI: 10.1039/c8cp03786h

    Structural differences between unannealed and expanded high-density amorphous ice based on isotope substitution neutron diffraction
    journal, August 2019

    Crucial role of fragmented and isolated defects in persistent relaxation of deeply supercooled water
    journal, September 2018

    • Saito, Shinji; Bagchi, Biman; Ohmine, Iwao
    • The Journal of Chemical Physics, Vol. 149, Issue 12
    • DOI: 10.1063/1.5044458

    Identification of structural relaxation in the dielectric response of water
    text, January 2016

    Nature of Water’s Second Glass Transition Elucidated by Doping and Isotope Substitution Experiments
    journal, January 2019

    • Fuentes-Landete, Violeta; Plaga, Lucie J.; Keppler, Markus
    • Physical Review X, Vol. 9, Issue 1
    • DOI: 10.1103/physrevx.9.011015

    Origin of the emergent fragile-to-strong transition in supercooled water
    journal, September 2018

    • Shi, Rui; Russo, John; Tanaka, Hajime
    • Proceedings of the National Academy of Sciences, Vol. 115, Issue 38
    • DOI: 10.1073/pnas.1807821115

    Common microscopic structural origin for water’s thermodynamic and dynamic anomalies
    journal, December 2018

    • Shi, Rui; Russo, John; Tanaka, Hajime
    • The Journal of Chemical Physics, Vol. 149, Issue 22
    • DOI: 10.1063/1.5055908

    Amorphous and crystalline ices studied by dielectric spectroscopy
    journal, June 2019

    • Plaga, L. J.; Raidt, A.; Fuentes Landete, V.
    • The Journal of Chemical Physics, Vol. 150, Issue 24
    • DOI: 10.1063/1.5100785

    Diffusive dynamics during the high-to-low density transition in amorphous ice
    journal, June 2017

    • Perakis, Fivos; Amann-Winkel, Katrin; Lehmkühler, Felix
    • Proceedings of the National Academy of Sciences, Vol. 114, Issue 31
    • DOI: 10.1073/pnas.1705303114

    Nuclear quantum effects on the liquid–liquid phase transition of a water-like monatomic liquid
    journal, January 2018

    • Nguyen, Binh; Lopez, Gustavo E.; Giovambattista, Nicolas
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 12
    • DOI: 10.1039/c7cp08505b

    Water: A Tale of Two Liquids
    journal, April 2016

      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: