Transport properties of glass-forming liquids suggest that dynamic crossover temperature is as important as the glass transition temperature

Mallamace, Francesco; Branca, C.; Corsaro, Carmelo; Leone, Nancy; Spooren, Jeroen; Chen, Sow‐Hsin; Stanley, H. Eugene

doi:10.1073/pnas.1015340107

Cited by 210 publications

(260 citation statements)

References 47 publications

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“…MDS of another water model (mW) find a crossover from ζ = −1 to ζ = −0.75 (62). The overall picture is that a similar crossover in the FSE exponent is observed for real water, simulations of water models (37,38,62), and experiments on ortho-terphenyl (23,24), Tris-naphthylbenzene (27), and seven other liquids (58). In the case of rotation, we find that FSED experimentally holds with a single exponent ζ = 0.97 over more than 2 decades.…”

Section: Resultssupporting

confidence: 48%

“…The FSE relation has since been tested for a variety of liquids and found to give a good description far from the glass transition (57). A putative universal crossover from FSE with ζ = −1 to ζ ' −0.85 upon cooling was suggested by the analysis of data for nine liquids (58). Simulations of models of supercooled fragile liquids (East models) find ζ ' −0.7 to −0.8 (59,60).…”

Section: Resultsmentioning

confidence: 99%

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Viscosity of deeply supercooled water and its coupling to molecular diffusion

Dehaoui

Issenmann

Caupin

2015

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

204

213

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The viscosity of a liquid measures its resistance to flow, with consequences for hydraulic machinery, locomotion of microorganisms, and flow of blood in vessels and sap in trees. Viscosity increases dramatically upon cooling, until dynamical arrest when a glassy state is reached. Water is a notoriously poor glassformer, and the supercooled liquid crystallizes easily, making the measurement of its viscosity a challenging task. Here we report viscosity of water supercooled close to the limit of homogeneous crystallization. Our values contradict earlier data. A single power law reproduces the 50-fold variation of viscosity up to the boiling point. Our results allow us to test the Stokes-Einstein and Stokes-Einstein-Debye relations that link viscosity, a macroscopic property, to the molecular translational and rotational diffusion, respectively. In molecular glassformers or liquid metals, the violation of the Stokes-Einstein relation signals the onset of spatially heterogeneous dynamics and collective motions. Although the viscosity of water strongly decouples from translational motion, a scaling with rotational motion remains, similar to canonical glassformers.supercooled water | viscosity | Stokes-Einstein relations W ater, considered as a potential glassformer, has been a longlasting topic of intense activity. Its possible liquid-glass transition was reported 50 years ago to be in the vicinity of 140 K (1, 2). However, ice nucleation hinders the access to this transition from the liquid side. Bypassing crystallization requires hyperquenching the liquid at tremendous cooling rates, ca. 10 7 K · s −1 (3). As a consequence, many questions about supercooled and glassy water and its glass-liquid transition remain open (4-7).As an example, crystallization of water is accompanied by one of the largest known relative changes in sound velocity, which has been attributed to the relaxation effects of the hydrogen bond network (8, 9). Indeed, whereas the sound velocity is around 1,400 m · s −1 in liquid water at 273 K, it reaches around 3,300 m · s −1 in ice at 273 K and a similar value in the known amorphous phases of ice at 80 K (10). Such a large jump is usually the signature of a strong glass, i.e., one in which relaxation times or viscosity follow an Arrhenius law upon cooling. However, pioneering measurements on bulk supercooled water by NMR (11) and quasi-elastic neutron scattering (12), as well as recent ones by optical Kerr effect (8, 9), reveal a large super-Arrhenius behavior between 340 and 240 K, similar to what is observed in fragile glassformers (13,14). The temperature dependence of the relaxation time is well described by a power law (8, 9), as expected from mode-coupling theory (15, 16), which usually applies well to liquids with a small change of sound velocity upon vitrification. Based on these and other observations, it has been hypothesized that supercooled water experiences a fragile-tostrong transition (17). This idea has motivated experimental efforts to measure dynamic properties of supercooled wate...

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Section: Resultssupporting

confidence: 48%

Section: Resultsmentioning

confidence: 99%

Viscosity of deeply supercooled water and its coupling to molecular diffusion

Dehaoui

Issenmann

Caupin

2015

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

204

213

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“…This behavior is seen in the physical properties of all glass-forming systems (and supercooled liquids)-structural relaxation allows a transition from the viscous to the elastic regime. It was recently shown that structural relaxation causes the transport properties of all supercooled liquids to be characterized by a dynamic crossover from super-Arrhenius to Arrhenius behavior (41). Using mode coupling to examine the hopping processes among these relaxing structures (39) we find the crossover temperature of the transition from liquidlike to solidlike behavior toward dynamic arrest (or glass transition).…”

Section: Methodsmentioning

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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“…The temperature associated with this overlap separates the lowtemperature Arrhenius behavior, typical for a glass, from the high-temperature super-exponential behavior, typical for a supercooled liquid. Both are separated by the crossover temperature * that unlike the glass transition temperature does not depend on the cooling rate 37,38 . In literature, this transition is sometimes referred to as fragile-to-strong (FTS) transition upon cooling 39 .…”

Section: Figmentioning

confidence: 99%

How Supercooled Liquid Phase-Change Materials Crystallize: Snapshots after Femtosecond Optical Excitation

et al. 2015

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Glass forming materials are employed in information storage technologies making use of the transition between a disordered (amorphous) and an ordered (crystalline) state. With increasing temperature the crystal growth velocity of these phase-change materials becomes so fast that prior studies have not been able to resolve these crystallization dynamics. However, crystallization is the time limiting factor in the write speed of phase-change memory devices. Here, for the first time, we quantify crystal growth velocities up to the melting point by using the relaxation of photo-excited carriers as an ultrafast heating mechanism.During repetitive femtosecond optical excitation, each pulse enables dynamical evolution for tens of picoseconds before the intermediate atomic structure is frozen-in as the sample rapidly cools. We apply this technique to Ag 4 In 3 Sb 67 Te 26 (AIST) and compare the dynamics of as-deposited and application-relevant melt-quenched glass. Both glasses retain their different kinetics even in the supercooled liquid state, thereby revealing differences in their kinetic fragilities. This approach enables the characterization of application-relevant properties of phase-change materials up to the melting temperature, which has not been possible before.Mankind has utilized glasses during the last five thousand years. They can be prepared by cooling a liquid fast and far enough below the glass transition temperature -to a temperature where its viscosity is sufficiently high that the atomic arrangement is kinetically frozen-in 1 . Until recently, research and technology have focused on good glass formers, i.e. materials which can be vitrified by cooling their liquid state at moderate rates. But in recent decades poor glass formers such as metallic glasses and certain chalcogenide glasses have gained interest due to their remarkable property portfolio 2,3 . These materials need to be cooled at rates in excess of around 3*10 9 K/s to bypass crystallization and to quench the atoms in an amorphous arrangement 4 . This so-called glass transition at temperature is commonly observed at a

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Transport properties of glass-forming liquids suggest that dynamic crossover temperature is as important as the glass transition temperature

Cited by 210 publications

References 47 publications

Viscosity of deeply supercooled water and its coupling to molecular diffusion

Viscosity of deeply supercooled water and its coupling to molecular diffusion

Possible relation of water structural relaxation to water anomalies

How Supercooled Liquid Phase-Change Materials Crystallize: Snapshots after Femtosecond Optical Excitation

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