Disruption of Hydrogen-Bonding Network Eliminates Water Anomalies Normally Observed on Cooling to Its Calorimetric Glass Transition

Jose M. Borreguero; Eugene Mamontov

doi:10.1021/acs.jpcb.7b01226

Disruption of Hydrogen-Bonding Network Eliminates Water Anomalies Normally Observed on Cooling to Its Calorimetric Glass Transition

Jose M. Borreguero, Eugene Mamontov

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Abstract

The calorimetric glass-transition temperature of water is 136 K, but extrapolation of thermodynamic and relaxation properties of water from ambient temperature to below its homogeneous nucleation temperature T_H = 235 K predicts divergence at T_S = 228 K. The "no-man's land" between the T_H and glassy water crystallization temperature of 150 K, which is encountered on warming up from the vitrified state, precludes a straightforward reconciliation of the two incompatible temperature dependences of water properties, above 235 K and below 150 K. The addition of lithium chloride to water allows bypassing both T_H and T_S on cooling, resulting in the dynamics with no features except the calorimetric glass transition, still at 136 K. We show that lithium chloride prevents hydrogen-bonding network completion in water on cooling, as manifested, in particular, in changing microscopic diffusion mechanism of the water molecules. Thus thermodynamic and relaxation peculiarities exhibited by pure water on cooling to its glass transition, such as the existence of the T_H and T_S, must be associated specifically with the hydrogen-bonding network.

Original language	English
Pages (from-to)	4168-4173
Number of pages	6
Journal	Journal of Physical Chemistry B
Volume	121
Issue number	16
DOIs	https://doi.org/10.1021/acs.jpcb.7b01226
State	Published - Apr 27 2017

Funding

The neutron scattering experiments on BASIS at SNS were supported by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. ORNL is managed by UT-Battelle, LLC, for the U.S. Department of Energy (DOE) under contract no. DE-AC05-00OR22725. J.M.B. is supported by the Center for Accelerating Materials Modeling (CAMM) funded by the U.S. Department of Energy, Basic Energy Sciences, Material Sciences and Engineering Division under FWP-3ERKCSNL. This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05- 00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy. gov/downloads/doe-public-access-plan).

Funders	Funder number
Center for Accelerating Materials Modeling
DOE Public Access Plan
Scientific User Facilities Division
United States Government
U.S. Department of Energy
Basic Energy Sciences	DE-AC05-00OR22725, FWP-3ERKCSNL
Oak Ridge National Laboratory

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10.1021/acs.jpcb.7b01226

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title = "Disruption of Hydrogen-Bonding Network Eliminates Water Anomalies Normally Observed on Cooling to Its Calorimetric Glass Transition",

abstract = "The calorimetric glass-transition temperature of water is 136 K, but extrapolation of thermodynamic and relaxation properties of water from ambient temperature to below its homogeneous nucleation temperature TH = 235 K predicts divergence at TS = 228 K. The {"}no-man's land{"} between the TH and glassy water crystallization temperature of 150 K, which is encountered on warming up from the vitrified state, precludes a straightforward reconciliation of the two incompatible temperature dependences of water properties, above 235 K and below 150 K. The addition of lithium chloride to water allows bypassing both TH and TS on cooling, resulting in the dynamics with no features except the calorimetric glass transition, still at 136 K. We show that lithium chloride prevents hydrogen-bonding network completion in water on cooling, as manifested, in particular, in changing microscopic diffusion mechanism of the water molecules. Thus thermodynamic and relaxation peculiarities exhibited by pure water on cooling to its glass transition, such as the existence of the TH and TS, must be associated specifically with the hydrogen-bonding network.",

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N2 - The calorimetric glass-transition temperature of water is 136 K, but extrapolation of thermodynamic and relaxation properties of water from ambient temperature to below its homogeneous nucleation temperature TH = 235 K predicts divergence at TS = 228 K. The "no-man's land" between the TH and glassy water crystallization temperature of 150 K, which is encountered on warming up from the vitrified state, precludes a straightforward reconciliation of the two incompatible temperature dependences of water properties, above 235 K and below 150 K. The addition of lithium chloride to water allows bypassing both TH and TS on cooling, resulting in the dynamics with no features except the calorimetric glass transition, still at 136 K. We show that lithium chloride prevents hydrogen-bonding network completion in water on cooling, as manifested, in particular, in changing microscopic diffusion mechanism of the water molecules. Thus thermodynamic and relaxation peculiarities exhibited by pure water on cooling to its glass transition, such as the existence of the TH and TS, must be associated specifically with the hydrogen-bonding network.

AB - The calorimetric glass-transition temperature of water is 136 K, but extrapolation of thermodynamic and relaxation properties of water from ambient temperature to below its homogeneous nucleation temperature TH = 235 K predicts divergence at TS = 228 K. The "no-man's land" between the TH and glassy water crystallization temperature of 150 K, which is encountered on warming up from the vitrified state, precludes a straightforward reconciliation of the two incompatible temperature dependences of water properties, above 235 K and below 150 K. The addition of lithium chloride to water allows bypassing both TH and TS on cooling, resulting in the dynamics with no features except the calorimetric glass transition, still at 136 K. We show that lithium chloride prevents hydrogen-bonding network completion in water on cooling, as manifested, in particular, in changing microscopic diffusion mechanism of the water molecules. Thus thermodynamic and relaxation peculiarities exhibited by pure water on cooling to its glass transition, such as the existence of the TH and TS, must be associated specifically with the hydrogen-bonding network.

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Disruption of Hydrogen-Bonding Network Eliminates Water Anomalies Normally Observed on Cooling to Its Calorimetric Glass Transition

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