Scaling concepts for the dynamics of viscous liquids near an ideal glassy state

Kirkpatrick, T. R.; Thirumalai, D.; Wolynes, Peter G.

doi:10.1103/physreva.40.1045

Cited by 1,013 publications

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References 33 publications

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“…The universal features of the dynamics of supercooled liquids and glasses are explained by the random first order transition theory 1,25,37,38 . At the mean field theory level the underlying microscopic framework provides a description of several characteristic transition temperatures that are expected in glassy systems.…”

Section: Theory Microscopic Theories Of the Glass And Liquidmentioning

confidence: 99%

Intermolecular Forces and the Glass Transition

Hall

Wolynes

2007

J. Phys. Chem. B

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Random first order transition theory is used to determine the role of attractive and repulsive interactions in the dynamics of supercooled liquids. Self-consistent phonon theory, an approximate mean field treatment consistent with random first order transition theory, is used to treat individual glassy configurations, while the liquid phase is treated using common liquid state approximations.Free energies are calculated using liquid state perturbation theory. The transition temperature T * A , the temperature where the onset of activated behavior is predicted by mean field theory, the lower crossover temperature T * c where barrierless motions actually occur through fractal or stringy motions (corresponding to the phenomenological mode coupling transition temperature), and T * K , the Kauzmann temperature (corresponding to an extrapolated entropy crisis), are calculated in addition to T * g , the glass transition temperature that corresponds to laboratory cooling rates. Relationships between these quantities agree well with existing experimental and simulation data on van der Waals liquids. Both the isobaric and isochoric behavior in the supercooled regime are studied, providing results for ∆C V and ∆C p that can be used to calculate the fragility as a function of density and pressure, respectively. The predicted variations in the α-relaxation time with temperature and density conform to the empirical density-temperature scaling relations found by Casalini and Roland. We thereby demonstrate the microscopic origin of their observations. Finally, the relationship first suggested by Sastry between the spinodal temperature and the Kauzmann temperatures, as a function of density, is examined. The present microscopic calculations support the existence of an intersection of these two temperatures at sufficiently low temperatures.2

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Section: Theory Microscopic Theories Of the Glass And Liquidmentioning

confidence: 99%

Intermolecular Forces and the Glass Transition

Hall

Wolynes

2007

J. Phys. Chem. B

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“…The statistics of these fluctuating local energies require that δΦ(δN ) ∼ Φ 0 √ δN , where Φ 0 is δN -independent, echoing the fluctuation statistics of the frozen random field of the RFIM. Thus, as (Kirkpatrick et al, 1989) suggest, the originally thin flat interface will become diffuse yielding x = 1/2. In the liquid case, a vivid interpretation of the surface energy renormalization is possible: Since the interface is distorted down to the smallest scale (allowed by the material's discretness), the region occupied by the now diffuse wall is neither of the two original structures it separates.…”

Section: N=7 N=5mentioning

confidence: 99%

“…At a crude level, this picture underlies the arguments from (Adam and Gibbs, 1965), but those arguments fail to relate the size of the moving regions to the energy landscape itself. In contrast, the Random First Order Transition (RFOT) theory (Kirkpatrick et al, 1989;Xia and Wolynes, 2000) explicitly shows how these reconfigurational motions occur and thus establishes intrinsic connection between the kinetic properties and the thermodynamics of supercooled liquids. Our account is based on (Lubchenko and Wolynes, 2004) which also discusses the intrinsic connection between cooperative, activated motions in the supercooled liquid both above and the classical aging dynamics below the glass transition.…”

Section: Overview Of the Classical Theory Of The Structural Glassmentioning

confidence: 99%

“…To a mathematician, this is a generalized problem of packing compact interacting objects of comparable size given a specific constraint on the density distribution (it is not periodic) and total energy of the system. A nearly complete conceptual, microscopic picture of the amorphous state has emerged in the course of the two last decades (Stoessel and Wolynes, 1984) (Singh et al, 1985) (Kirkpatrick and Wolynes, 1987a,b) ( Kirkpatrick and Thirumalai, 1987a,b;Kirkpatrick et al, 1989) Wolynes, 2000, 2001a,b) (Lubchenko and Wolynes, 2001, 2003a,b, 2004. This framework has lead to a unified, quantitative understanding of many seemingly unrelated phenomena in supercooled liquids above and below the glass transition.…”

Section: Overview Of the Classical Theory Of The Structural Glassmentioning

confidence: 99%

“…As the temperature is lowered further, the relaxation barriers grow in a very dramatic fashion thus confining the molecules in their metastable arrangements long enough to give the appearance of shear elasticity in the sample on the technologically relevant frequency scales. A quantitative understanding of the physics behind the glass transition has recently been achieved with the random first order transition (RFOT) theory of glasses (Kirkpatrick et al, 1989;Xia and Wolynes, 2000). This theory has provided a microscopic picture of molecular motions in supercooled liquids, such as first principle predictions of the length scales of these motions and the cooperativity lengths and the barrier heights of the activated transport.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

The Microscopic Quantum Theory of Low Temperature Amorphous Solids

Lubchenko¹,

Wolynes²

2007

Advances in Chemical Physics

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The quantum excitations in glasses have long presented a set of puzzles for condensed matter physicists. A common view is that they are largely disordered analogs of elementary excitations in crystals, supplemented by two level systems which are chemically local entities coming from disorder. A radical revision of this picture argues that the excitations in low temperature glasses are deeply connected to the energy landscape of the glass when it vitrifies: the excitations are not low excited states built on a single ground state but locally defined resonances, high in the energy spectrum of a solid. According to a semiclassical analysis, the two level systems involve resonant collective tunneling motions of around two hundred molecular units which are relics of the mosaic of cooperative motions at the glass transition temperature Tg. The density of states of the TLS is determined by Tg and the mosaic's length scale, which is a weak function of the cooling rate. The universality of phonon scattering in insulating glasses is explained. The Boson Peak and the plateau in thermal conductivity, observed at higher temperatures, are also quantitatively understood within the picture as arising from the same cooperative motions, but now accompanied by thermal activation of the mosaic's vibrational modes. The dynamics of some of the local structural transitions have significant quantum corrections to the semiclassical picture. These corrections lead to a deviation of the heat capacity and conductivity from the standard tunneling model results and explain the anomalous time dependence of the heat capacity. Interaction between tunneling centers contributes to the large and negative value of the Grüneisen parameter often observed in glasses.

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Physical Aging of Polymers

Cangialosi

2018

Encyclopedia of Polymer Science and Technology

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This article provides an overview of the most important aspects of physical aging of polymers. First, we briefly introduce basic concepts of the glass transition, that is, the way a nonequilibrium glass is formed. Subsequently, after presenting the way physical aging can be monitored, we describe the main well‐established signatures of physical aging, that is, its nonexponential and nonlinear nature. The next part of the article is dedicated to recent advancements in the physical aging of bulk polymers. In this context, recent experimental activity is discussed, where the existence of multiple mechanisms for equilibrium recovery is presented. In addition, important aspects of physical aging in polymers altered by geometrical confinement are scrutinized in light of the past 20 years efforts aiming to understand glass dynamics in such conditions. It is shown how confined polymers weakly interacting with the confining medium exhibit accelerated physical aging. Importantly, such acceleration was found to be decoupled from the molecular mobility of the glass. Finally, we briefly discuss how recent advancements in physical aging of polymers in bulk and under geometrical confinement should foster experimental efforts to unveil important basic aspects of the glass transition, such as the existence of the so‐called “ideal glass.”

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Scaling concepts for the dynamics of viscous liquids near an ideal glassy state

Cited by 1,013 publications

References 33 publications

Intermolecular Forces and the Glass Transition

Intermolecular Forces and the Glass Transition

The Microscopic Quantum Theory of Low Temperature Amorphous Solids

Physical Aging of Polymers

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