Isomorph theory of physical aging

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

Resumé

This paper derives and discusses the configuration-space Langevin equation describing a physically aging R-simple system and the corresponding Smoluchowski equation. Externally controlled thermodynamic variables like temperature, density, and pressure enter the description via the single parameter Ts/T, in which T is the bath temperature and Ts is the “systemic” temperature defined at any time t as the thermodynamic equilibrium temperature of the state point with density ρ(t) and potential energy U(t). In equilibrium, Ts ≅ T with fluctuations that vanish in the thermodynamic limit. In contrast to Tool’s fictive temperature and other effective temperatures in glass science, the systemic temperature is defined for any configuration with a well-defined density, even if it is not close to equilibrium. Density and systemic temperature define an aging phase diagram, in which the aging system traces out a curve. Predictions are discussed for aging following various density-temperature and pressure-temperature jumps from one equilibrium state to another, as well as for a few other scenarios. The proposed theory implies that R-simple glass-forming liquids are characterized by the dynamic Prigogine-Defay ratio being equal to unity
OriginalsprogEngelsk
Artikelnummer154502
TidsskriftJournal of Chemical Physics
Vol/bind148
ISSN0021-9606
DOI
StatusUdgivet - 2018

Citer dette

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title = "Isomorph theory of physical aging",
abstract = "This paper derives and discusses the configuration-space Langevin equation describing a physically aging R-simple system and the corresponding Smoluchowski equation. Externally controlled thermodynamic variables like temperature, density, and pressure enter the description via the single parameter Ts/T, in which T is the bath temperature and Ts is the “systemic” temperature defined at any time t as the thermodynamic equilibrium temperature of the state point with density ρ(t) and potential energy U(t). In equilibrium, Ts ≅ T with fluctuations that vanish in the thermodynamic limit. In contrast to Tool’s fictive temperature and other effective temperatures in glass science, the systemic temperature is defined for any configuration with a well-defined density, even if it is not close to equilibrium. Density and systemic temperature define an aging phase diagram, in which the aging system traces out a curve. Predictions are discussed for aging following various density-temperature and pressure-temperature jumps from one equilibrium state to another, as well as for a few other scenarios. The proposed theory implies that R-simple glass-forming liquids are characterized by the dynamic Prigogine-Defay ratio being equal to unity",
author = "Jeppe Dyre",
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Isomorph theory of physical aging. / Dyre, Jeppe.

I: Journal of Chemical Physics, Bind 148, 154502, 2018.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Isomorph theory of physical aging

AU - Dyre, Jeppe

PY - 2018

Y1 - 2018

N2 - This paper derives and discusses the configuration-space Langevin equation describing a physically aging R-simple system and the corresponding Smoluchowski equation. Externally controlled thermodynamic variables like temperature, density, and pressure enter the description via the single parameter Ts/T, in which T is the bath temperature and Ts is the “systemic” temperature defined at any time t as the thermodynamic equilibrium temperature of the state point with density ρ(t) and potential energy U(t). In equilibrium, Ts ≅ T with fluctuations that vanish in the thermodynamic limit. In contrast to Tool’s fictive temperature and other effective temperatures in glass science, the systemic temperature is defined for any configuration with a well-defined density, even if it is not close to equilibrium. Density and systemic temperature define an aging phase diagram, in which the aging system traces out a curve. Predictions are discussed for aging following various density-temperature and pressure-temperature jumps from one equilibrium state to another, as well as for a few other scenarios. The proposed theory implies that R-simple glass-forming liquids are characterized by the dynamic Prigogine-Defay ratio being equal to unity

AB - This paper derives and discusses the configuration-space Langevin equation describing a physically aging R-simple system and the corresponding Smoluchowski equation. Externally controlled thermodynamic variables like temperature, density, and pressure enter the description via the single parameter Ts/T, in which T is the bath temperature and Ts is the “systemic” temperature defined at any time t as the thermodynamic equilibrium temperature of the state point with density ρ(t) and potential energy U(t). In equilibrium, Ts ≅ T with fluctuations that vanish in the thermodynamic limit. In contrast to Tool’s fictive temperature and other effective temperatures in glass science, the systemic temperature is defined for any configuration with a well-defined density, even if it is not close to equilibrium. Density and systemic temperature define an aging phase diagram, in which the aging system traces out a curve. Predictions are discussed for aging following various density-temperature and pressure-temperature jumps from one equilibrium state to another, as well as for a few other scenarios. The proposed theory implies that R-simple glass-forming liquids are characterized by the dynamic Prigogine-Defay ratio being equal to unity

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DO - 10.1063/1.5022999

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VL - 148

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

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