Singularity-free interpretation of the thermodynamics of supercooled water

Sastry, Srikanth; Debenedetti, Pablo G.; Sciortino, Francesco; Stanley, H. Eugene

doi:10.1103/physreve.53.6144

Cited by 541 publications

(635 citation statements)

References 27 publications

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“…There have been three hypotheses about a unified picture of water and its anomalous behavior: the stability limit hypothesis 183 , the singularity-free hypothesis 184 , and the liquid-liquid phase-transition hypothesis 185 . However, there are severe experimental limitations in accessing the region of the phase diagram that could usefully discriminate among these hypotheses.…”

Section: Water Structure Away From Ambient Conditionsmentioning

confidence: 99%

Water Structure from Scattering Experiments and Simulation

2002

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Section: Water Structure Away From Ambient Conditionsmentioning

confidence: 99%

Water Structure from Scattering Experiments and Simulation

2002

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“…There are four current hypotheses (1), two of which have gained considerable attention: the singularity-free hypothesis (3,4) and the liquid-liquid critical point (LLCP) hypothesis (5). The LLCP hypothesis is based on two assumptions: (i) that water displays the phenomenon of "liquid polymorphism" (6) and (ii) as T decreases, the hydrogen bonds (HBs) begin to form an open tetrahedrally coordinated HB network.…”

mentioning

confidence: 99%

Possible relation of water structural relaxation to water anomalies

Mallamace

Corsaro

Stanley

2013

Proc. Natl. Acad. Sci. U.S.A.

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The anomalous behavior of thermodynamic response functions is an unsolved problem in the physics of water. The mechanism that gives rise to the dramatic indefinite increase at low temperature in the heat capacity, the compressibility, and the coefficient of thermal expansion, is unknown. We explore this problem by analyzing both new and existing experimental data on the power spectrum S(Q, ω) of bulk and confined water at ambient pressure. When decreasing the temperature, we find that the liquid undergoes a structural transformation coinciding with the onset of an extended hydrogen bond network. This network onset seems to give rise to the marked viscoelastic behavior, consistent with the interesting possibility that the sound velocity and response functions of water depend upon both the frequency and wave vector.A lthough water is one of the simplest molecules, it is in reality a very complex liquid displaying more than 64 counterintuitive anomalies, most of which have not been adequately explained (1, 2). The best known of these is its density behavior: unlike most liquids, water displays a maximum at 4°C, and becomes less dense rather than more dense when it freezes. Other unexplained anomalies occur for response functions such as the isothermal compressibility K T , the isobaric heat capacity C P , and the thermal expansion coefficient α P . Moreover, if one extrapolates these functions into the metastable supercooled phase of water below the melting temperature (T M = 273 K at atmospheric pressure), and above the homogeneous nucleation temperature (T H ∼ 231 K), they behave as if they might diverge at a singular temperature T S ∼ 228 K (1). Water is a glassy liquid below the glass transition temperature T g ∼ 130 K (2). Immediately above T g it transforms into a highly viscous fluid and ultimately crystallizes at T X ∼ 150 K. The region between T X and T H is a "no-man's land" within which bulk liquid water cannot be studied (1). For these and other reasons, liquid water is one of the most exciting research topics, and an enormous number of studies have sought to elucidate the physical reasons for water's unusual properties.There are four current hypotheses (1), two of which have gained considerable attention: the singularity-free hypothesis (3, 4) and the liquid-liquid critical point (LLCP) hypothesis (5). The LLCP hypothesis is based on two assumptions: (i) that water displays the phenomenon of "liquid polymorphism" (6) and (ii) as T decreases, the hydrogen bonds (HBs) begin to form an open tetrahedrally coordinated HB network. If we begin with the stable liquid phase and decrease T, the HB lifetime and the cluster stability increase, and this altered local structure continues through the no-man's land down to the amorphous phase region. Amorphous solid water is widely believed to display polymorphism: below T g , low-density amorphous (LDA) and high-density amorphous (HDA) structures (7) can be transformed from one to the other by tuning the pressure. Hence liquid water may have local structural features...

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“…F. Caupin expects his measurements to discriminate between two different theories, the one by R. Speedy et al [8] and the one by S.Sastry et al [9].…”

Section: Acoustic Cavitationmentioning

confidence: 99%

Acoustics and metastable liquids

Balibar

2004

Europhysics News

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Singularity-free interpretation of the thermodynamics of supercooled water

Cited by 541 publications

References 27 publications

Water Structure from Scattering Experiments and Simulation

Water Structure from Scattering Experiments and Simulation

Possible relation of water structural relaxation to water anomalies

Acoustics and metastable liquids

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