Supercooled and glassy water

Debenedetti, Pablo G.

doi:10.1088/0953-8984/15/45/r01

Cited by 1,088 publications

(1,178 citation statements)

References 308 publications

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“…5(a), path b]. In a real experiment, this discontinuous change may not occur at the coexistence line since a substance can remain in a supercooled metastable phase until a limit of stability (a spinodal) is reached [15] [ Fig. 5(b), path b].…”

Section: The Widom Linementioning

confidence: 99%

“…This asymptotic line is sometimes called the Widom line, and is often regarded as an extension of the coexistence line into the ''one-phase regime.'' Water's anomalies have been hypothesized to be related to the existence of a line of a first-order liquid-liquid phase transition terminating at a liquid-liquid critical point [10,13,15,16], located below the homogeneous nucleation line in the deep supercooled region of the phase diagram-sometimes called the ''no-man's land'' because it is difficult to make direct measurements on the bulk liquid phase [13]. In supercooled water, the liquid-liquid coexistence line and the Widom line have negative slopes.…”

Section: The Widom Linementioning

confidence: 99%

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The puzzling unsolved mysteries of liquid water: Some recent progress

Stanley

Kumar

et al. 2007

Physica A: Statistical Mechanics and its Applications

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Water is perhaps the most ubiquitous, and the most essential, of any molecule on earth. Indeed, it defies the imagination of even the most creative science fiction writer to picture what life would be like without water. Despite decades of research, however, water's puzzling properties are not understood and 63 anomalies that distinguish water from other liquids remain unsolved. We introduce some of these unsolved mysteries, and demonstrate recent progress in solving them. We present evidence from experiments and computer simulations supporting the hypothesis that water displays a special transition point (which is not unlike the ''tipping point'' immortalized by Malcolm Gladwell). The general idea is that when the liquid is near this ''tipping point,'' it suddenly separates into two distinct liquid phases. This concept of a new critical point is finding application to other liquids as well as water, such as silicon and silica. We also discuss related puzzles, such as the mysterious behavior of water near a protein. r

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Section: The Widom Linementioning

confidence: 99%

Section: The Widom Linementioning

confidence: 99%

The puzzling unsolved mysteries of liquid water: Some recent progress

Stanley

Kumar

et al. 2007

Physica A: Statistical Mechanics and its Applications

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“…As the temperature is lowered, macroscopic properties of water, such as density, compressibility, thermal expansion coefficient and heat capacity, seem to deviate from those of simple liquids. 1 The origin of these unusual properties lies in the fact that the H 2 O molecule acts both as a donor and acceptor, 2 leading to the formation of a random three dimensional hydrogen bonding network which fluctuates on ultrafast timescales. In liquid water, depending on the temperature, this may give rise to different hydrogen bonding motifs, which at ambient conditions seem to coexist as structural and dynamic heterogeneities.…”

Section: Introductionmentioning

confidence: 99%

Two-Dimensional Infrared Spectroscopy of Supercooled Water

Perakis

Hamm

2010

J. Phys. Chem. B

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We present two-dimensional infrared (2D IR) spectra of the OD stretch vibration of isotope diluted water (HOD/H2O) from ambient conditions (293 K) down to the metastable supercooled regime (260 K). We observe that spectral diffusion slows down from 700 fs to 2.6 ps as we lower the temperature. A comparison between measurements performed at the magic angle with those at parallel polarization shows that the 2D IR line shape is affected by the frequency-dependent anisotropy decay in the case of parallel polarization, altering the extracted correlation decay. A fit within the framework of an Arrhenius law reveals an activation energy of Ea = 6.2 ± 0.2 kcal/mol and a pre-exponential factor of 1/A = 0.02 ± 0.01 fs. Alternatively, a power law fit results in an exponent γ = 2.2 and a singularity temperature Ts = 221 K. We tentatively conclude that the power law provides the better physical picture to describe the dynamics of liquid water around the freezing point. 2D IR spectroscopy of supercooled water AbstractWe present 2D IR spectra of the OD stretch vibration of isotope diluted water (HOD/H 2 O) from ambient conditions (293 K) down to the metastable supercooled regime (260 K). We observe that spectral diffusion slows down from 700 fs to 2.6 ps as we lower the temperature.Comparison between measurements performed at magic angle with those at parallel polarization shows that the 2D IR lineshape is affected by the frequency dependent anisotropy decay in the case of parallel polarization, altering the extracted correlation decay. A fit within the framework of an Arrhenius law reveals an activation energy of E a = 6.2 ± 0.2 kcal/mol and a pre-exponential factor of 1/A = 0.02 ± 0.01 fs. Alternatively, a power law fit results in an exponent γ = 2.2 and a singularity temperature T s = 221 K. We tentatively conclude that the power law provides the better physical picture to describe the dynamics of liquid water around the freezing point.

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“…Hydration water around biomolecules participates actively in biological function such as protein folding [2], and the complex interactions between biomolecules inside cells is mediated by the water solvent through the hydrophobic effect [3,4,5]. Supercooled water in the bulk and in confined geometries is also of large current interest due to the intriguing yet controversial possibility of a liquidliquid critical point in the deeply supercooled region [6,7,8]. On a larger scale, global climate change is affected by feedback loops involving water vapor -the most common greenhouse gas -and liquid water [9,10].…”

Section: Introductionmentioning

confidence: 99%

“…amorphous ice [18,19,20,21,22,8], premelted [23,24,25] and solid [26,27,28] surfaces and adsorbed overlayers. The correct description of such systems is in many cases beyond the computational capabilities of available ab initio methods.…”

Section: Introductionmentioning

confidence: 99%

A transferable H2O interaction potential based on a single center multipole expansion: SCME

Wikfeldt

Batista

Vila

et al. 2013

Phys. Chem. Chem. Phys.

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Abstract. A transferable potential energy function for describing the interaction between water molecules is presented. The electrostatic interaction is described rigorously using a multipole expansion. Only one expansion center is used per molecule to avoid the introduction of monopoles. This single center approach turns out to converge and give close agreement with ab initio calculations when carried out up to and including the hexadecapole. Both dipole and quadrupole polarizability is included. All parameters in the electrostatic interaction as well as the dispersion interaction are taken from ab initio calculations or experimental measurements of a single water molecule. The repulsive part of the interaction is parametrized to fit ab initio calculations of small water clusters and experimental measurements of ice I h . The parametrized potential function was then used to simulate liquid water and the results agree well with experiment, even better than simulations using some of the point charge potentials fitted to liquid water. The evaluation of the new interaction potential for condensed phases is fast because point charges are not present and the interaction can, to a good approximation, be truncated at a finite range.

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Supercooled and glassy water

Abstract: Cold, noncrystalline states play an important role in understanding the physics of liquid water. From recent experimental and theoretical investigations, a coherent interpretation of water's properties is beginning to emerge.

Cited by 1,088 publications

References 308 publications

The puzzling unsolved mysteries of liquid water: Some recent progress

The puzzling unsolved mysteries of liquid water: Some recent progress

Two-Dimensional Infrared Spectroscopy of Supercooled Water

A transferable H2O interaction potential based on a single center multipole expansion: SCME

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