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Title: Reversible structural transformations in supercooled liquid water from 135 to 245 K

Abstract

Water has many anomalous properties compared to “simple” liquids, and these anomalies are typically enhanced in supercooled water.1-3 While numerous models have been proposed, including the liquid-liquid critical point,4,5 the singularity-free scenario,6 and the stability limit conjecture,1 a molecular-level understanding remains elusive. The main difficulty in determining which, if any, of these models is correct is the limited amount of data in the relevant temperature and pressure ranges. For water at ambient pressures, which is the focus of this work, data is largely missing from 160 – 232 K (“No Man’s Land”) due to rapid crystallization.2,3 Whether rapid crystallization is just an experimental obstacle, or a fundamental problem signaling the inability of water to thermally equilibrate prior to crystallization is also a major unanswered question.5,7 Here, we investigate the structural transformations of transiently-heated, supercooled water with nanosecond time resolution using infrared vibrational spectroscopy. The experiments demonstrate three key results. First, water’s structure relaxes from its initial configuration to a “steady-state” configuration prior to the onset of crystallization over a wide temperature range. Second, water’s steady-state structure can be reproduced by a linear combination of two, temperature-independent structures that correspond to a “high-temperature liquid” and a “low-temperature liquid.” Third, the observedmore » structural changes are reversible over the full temperature range. Taken together, these results show that supercooled water can equilibrate prior to crystallization for temperatures from the homogeneous nucleation temperature, TH ~232 K,3 down to the glass transition temperature (Tg ~ 136 K). Second, the results provide support for the hypothesis that supercooled water can be described as a mixture of two, structurally-distinct, interconvertible liquids from 135 K to 245 K.5,8-18« less

Authors:
 [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1673601
Report Number(s):
PNNL-SA-150044
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Science
Additional Journal Information:
Journal Volume: 369; Journal Issue: 6510
Country of Publication:
United States
Language:
English

Citation Formats

Kringle, Loni M., Thornley, Wyatt A., Kay, Bruce D., and Kimmel, Gregory A. Reversible structural transformations in supercooled liquid water from 135 to 245 K. United States: N. p., 2020. Web. doi:10.1126/science.abb7542.
Kringle, Loni M., Thornley, Wyatt A., Kay, Bruce D., & Kimmel, Gregory A. Reversible structural transformations in supercooled liquid water from 135 to 245 K. United States. doi:10.1126/science.abb7542.
Kringle, Loni M., Thornley, Wyatt A., Kay, Bruce D., and Kimmel, Gregory A. Fri . "Reversible structural transformations in supercooled liquid water from 135 to 245 K". United States. doi:10.1126/science.abb7542.
@article{osti_1673601,
title = {Reversible structural transformations in supercooled liquid water from 135 to 245 K},
author = {Kringle, Loni M. and Thornley, Wyatt A. and Kay, Bruce D. and Kimmel, Gregory A.},
abstractNote = {Water has many anomalous properties compared to “simple” liquids, and these anomalies are typically enhanced in supercooled water.1-3 While numerous models have been proposed, including the liquid-liquid critical point,4,5 the singularity-free scenario,6 and the stability limit conjecture,1 a molecular-level understanding remains elusive. The main difficulty in determining which, if any, of these models is correct is the limited amount of data in the relevant temperature and pressure ranges. For water at ambient pressures, which is the focus of this work, data is largely missing from 160 – 232 K (“No Man’s Land”) due to rapid crystallization.2,3 Whether rapid crystallization is just an experimental obstacle, or a fundamental problem signaling the inability of water to thermally equilibrate prior to crystallization is also a major unanswered question.5,7 Here, we investigate the structural transformations of transiently-heated, supercooled water with nanosecond time resolution using infrared vibrational spectroscopy. The experiments demonstrate three key results. First, water’s structure relaxes from its initial configuration to a “steady-state” configuration prior to the onset of crystallization over a wide temperature range. Second, water’s steady-state structure can be reproduced by a linear combination of two, temperature-independent structures that correspond to a “high-temperature liquid” and a “low-temperature liquid.” Third, the observed structural changes are reversible over the full temperature range. Taken together, these results show that supercooled water can equilibrate prior to crystallization for temperatures from the homogeneous nucleation temperature, TH ~232 K,3 down to the glass transition temperature (Tg ~ 136 K). Second, the results provide support for the hypothesis that supercooled water can be described as a mixture of two, structurally-distinct, interconvertible liquids from 135 K to 245 K.5,8-18},
doi = {10.1126/science.abb7542},
journal = {Science},
number = 6510,
volume = 369,
place = {United States},
year = {2020},
month = {9}
}

Works referenced in this record:

Stability-limit conjecture. An interpretation of the properties of water
journal, March 1982

  • Speedy, Robin J.
  • The Journal of Physical Chemistry, Vol. 86, Issue 6
  • DOI: 10.1021/j100395a030

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

Water: A Tale of Two Liquids
journal, April 2016


Water Revisited
journal, July 1980


Unified description of temperature-dependent hydrogen-bond rearrangements in liquid water
journal, September 2005

  • Smith, J. D.; Cappa, C. D.; Wilson, K. R.
  • Proceedings of the National Academy of Sciences, Vol. 102, Issue 40
  • DOI: 10.1073/pnas.0506899102

The structural origin of anomalous properties of liquid water
journal, December 2015

  • Nilsson, Anders; Pettersson, Lars G. M.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9998

Is water one liquid or two?
journal, June 2019

  • Soper, A. K.
  • The Journal of Chemical Physics, Vol. 150, Issue 23
  • DOI: 10.1063/1.5096460

Phase behaviour of metastable water
journal, November 1992

  • Poole, Peter H.; Sciortino, Francesco; Essmann, Ulrich
  • Nature, Vol. 360, Issue 6402
  • DOI: 10.1038/360324a0

Metastable liquid–liquid transition in a molecular model of water
journal, June 2014

  • Palmer, Jeremy C.; Martelli, Fausto; Liu, Yang
  • Nature, Vol. 510, Issue 7505
  • DOI: 10.1038/nature13405

Singularity-free interpretation of the thermodynamics of supercooled water
journal, June 1996

  • Sastry, Srikanth; Debenedetti, Pablo G.; Sciortino, Francesco
  • Physical Review E, Vol. 53, Issue 6
  • DOI: 10.1103/PhysRevE.53.6144

The putative liquid-liquid transition is a liquid-solid transition in atomistic models of water
journal, October 2011

  • Limmer, David T.; Chandler, David
  • The Journal of Chemical Physics, Vol. 135, Issue 13
  • DOI: 10.1063/1.3643333

Structural transformation in supercooled water controls the crystallization rate of ice
journal, November 2011


Spatially inhomogeneous bimodal inherent structure of simulated liquid water
journal, January 2011

  • Wikfeldt, K. T.; Nilsson, A.; Pettersson, L. G. M.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 44
  • DOI: 10.1039/c1cp22076d

Relation between the Widom line and the dynamic crossover in systems with a liquid-liquid phase transition
journal, November 2005

  • Xu, L.; Kumar, P.; Buldyrev, S. V.
  • Proceedings of the National Academy of Sciences, Vol. 102, Issue 46
  • DOI: 10.1073/pnas.0507870102

Evidence of the existence of the low-density liquid phase in supercooled, confined water
journal, December 2006

  • Mallamace, F.; Broccio, M.; Corsaro, C.
  • Proceedings of the National Academy of Sciences, Vol. 104, Issue 2
  • DOI: 10.1073/pnas.0607138104

Entropy-driven liquid–liquid separation in supercooled water
journal, October 2012

  • Holten, V.; Anisimov, M. A.
  • Scientific Reports, Vol. 2, Issue 1
  • DOI: 10.1038/srep00713

Evidence of two distinct local structures of water from ambient to supercooled conditions
journal, September 2013

  • Taschin, A.; Bartolini, P.; Eramo, R.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3401

Ultrafast X-ray probing of water structure below the homogeneous ice nucleation temperature
journal, June 2014

  • Sellberg, J. A.; Huang, C.; McQueen, T. A.
  • Nature, Vol. 510, Issue 7505
  • DOI: 10.1038/nature13266

Understanding water’s anomalies with locally favoured structures
journal, April 2014

  • Russo, John; Tanaka, Hajime
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4556

Maxima in the thermodynamic response and correlation functions of deeply supercooled water
journal, December 2017


Pressure dependence of viscosity in supercooled water and a unified approach for thermodynamic and dynamic anomalies of water
journal, April 2017

  • Singh, Lokendra P.; Issenmann, Bruno; Caupin, Frédéric
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 17
  • DOI: 10.1073/pnas.1619501114

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

Perspective: Crossing the Widom line in no man’s land: Experiments, simulations, and the location of the liquid-liquid critical point in supercooled water
journal, October 2018

  • Hestand, Nicholas J.; Skinner, J. L.
  • The Journal of Chemical Physics, Vol. 149, Issue 14
  • DOI: 10.1063/1.5046687

Growth rate of crystalline ice and the diffusivity of supercooled water from 126 to 262 K
journal, December 2016

  • Xu, Yuntao; Petrik, Nikolay G.; Smith, R. Scott
  • Proceedings of the National Academy of Sciences, Vol. 113, Issue 52
  • DOI: 10.1073/pnas.1611395114

IR and Raman spectra of liquid water: Theory and interpretation
journal, June 2008

  • Auer, B. M.; Skinner, J. L.
  • The Journal of Chemical Physics, Vol. 128, Issue 22
  • DOI: 10.1063/1.2925258

Local statistical interpretation for water structure
journal, May 2013


Temperature Dependence of Inhomogeneous Broadening:  On the Meaning of Isosbestic Points
journal, October 2005

  • Geissler, Phillip L.
  • Journal of the American Chemical Society, Vol. 127, Issue 42
  • DOI: 10.1021/ja0545214

Growing correlation length in supercooled water
journal, June 2009

  • Moore, Emily B.; Molinero, Valeria
  • The Journal of Chemical Physics, Vol. 130, Issue 24
  • DOI: 10.1063/1.3158470

Corresponding states for mesostructure and dynamics of supercooled water
journal, January 2013


Homogeneous ice nucleation rates and crystallization kinetics in transiently-heated, supercooled water films from 188 K to 230 K
journal, May 2019

  • Kimmel, Greg A.; Xu, Yuntao; Brumberg, Alexandra
  • The Journal of Chemical Physics, Vol. 150, Issue 20
  • DOI: 10.1063/1.5100147

Intermediate range order in supercooled water
journal, February 2019


A nanosecond pulsed laser heating system for studying liquid and supercooled liquid films in ultrahigh vacuum
journal, April 2016

  • Xu, Yuntao; Dibble, Collin J.; Petrik, Nikolay G.
  • The Journal of Chemical Physics, Vol. 144, Issue 16
  • DOI: 10.1063/1.4947304

Homogeneous Nucleation of Ice in Transiently-Heated, Supercooled Liquid Water Films
journal, November 2017

  • Xu, Yuntao; Petrik, Nikolay G.; Smith, R. Scott
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 23
  • DOI: 10.1021/acs.jpclett.7b02685

Molecular-Scale Density Oscillations in Water Adjacent to a Mica Surface
journal, September 2001


Direct measurement of molecular forces
journal, March 1978

  • Derjaguin, B. V.; Rabinovich, Y. I.; Churaev, N. V.
  • Nature, Vol. 272, Issue 5651
  • DOI: 10.1038/272313a0

Molecular dynamics simulations of disjoining pressure effect in ultra-thin water film on a metal surface
journal, December 2013


Compatibility of quantitative X-ray spectroscopy with continuous distribution models of water at ambient conditions
journal, February 2019

  • Niskanen, Johannes; Fondell, Mattis; Sahle, Christoph J.
  • Proceedings of the National Academy of Sciences, Vol. 116, Issue 10
  • DOI: 10.1073/pnas.1815701116

Confined Water as Model of Supercooled Water
journal, March 2016


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

Mixturelike Behavior Near a Liquid-Liquid Phase Transition in Simulations of Supercooled Water
journal, March 2011


Thermodynamics of supercooled and stretched water: Unifying two-structure description and liquid-vapor spinodal
journal, July 2019

  • Caupin, Frédéric; Anisimov, Mikhail A.
  • The Journal of Chemical Physics, Vol. 151, Issue 3
  • DOI: 10.1063/1.5100228

The structure of water around the compressibility minimum
journal, December 2014

  • Skinner, L. B.; Benmore, C. J.; Neuefeind, J. C.
  • The Journal of Chemical Physics, Vol. 141, Issue 21
  • DOI: 10.1063/1.4902412

The inhomogeneous structure of water at ambient conditions
journal, August 2009

  • Huang, C.; Wikfeldt, K. T.; Tokushima, T.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 36
  • DOI: 10.1073/pnas.0904743106

Experimental evidence of low-density liquid water upon rapid decompression
journal, February 2018

  • Lin, Chuanlong; Smith, Jesse S.; Sinogeikin, Stanislav V.
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 9
  • DOI: 10.1073/pnas.1716310115

X-ray Scattering and O–O Pair-Distribution Functions of Amorphous Ices
journal, July 2018

  • Mariedahl, Daniel; Perakis, Fivos; Späh, Alexander
  • The Journal of Physical Chemistry B, Vol. 122, Issue 30
  • DOI: 10.1021/acs.jpcb.8b04823

Benchmark oxygen-oxygen pair-distribution function of ambient water from x-ray diffraction measurements with a wide Q -range
journal, February 2013

  • Skinner, Lawrie B.; Huang, Congcong; Schlesinger, Daniel
  • The Journal of Chemical Physics, Vol. 138, Issue 7
  • DOI: 10.1063/1.4790861

Intermediate range O–O correlations in supercooled water down to 235 K
journal, June 2019

  • Pathak, Harshad; Späh, Alexander; Kim, Kyung Hwan
  • The Journal of Chemical Physics, Vol. 150, Issue 22
  • DOI: 10.1063/1.5100811

X‐ray and neutron scattering studies of the structure of hyperquenched glassy water
journal, July 1992

  • Bellissent‐Funel, M. C.; Bosio, L.; Hallbrucker, A.
  • The Journal of Chemical Physics, Vol. 97, Issue 2
  • DOI: 10.1063/1.463254