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Journal of Chemical Physics / Volume 123 / Issue 3 / ARTICLES / Condensed Phase Dynamics, Structure, and Thermodynamics: Spectroscopy, Reactions, and Relaxation

J. Chem. Phys. 123, 034506 (2005); http://dx.doi.org/10.1063/1.1949211 (12 pages)

Two-Gaussian excitations model for the glass transition

Dmitry V. Matyushov and C. A. Angell

Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604

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(Received 20 April 2005; accepted 17 May 2005; published online 25 July 2005)

We develop a modified “two-state” model with Gaussian widths for the site energies of both ground and excited states, consistent with expectations for a disordered system. The thermodynamic properties of the system are analyzed in configuration space and found to bridge the gap between simple two-state models (“logarithmic” model in configuration space) and the random energy model (“Gaussian” model in configuration space). The Kauzmann singularity given by the random energy model remains for very fragile liquids but is suppressed or eliminated for stronger liquids. The sharp form of constant-volume heat capacity found by recent simulations for binary mixed Lennard-Jones and soft-sphere systems is reproduced by the model, as is the excess entropy and heat capacity of a variety of laboratory systems, strong and fragile. The ideal glass in all cases has a narrow Gaussian, almost invariant among molecular and atomic glassformers, while the excited-state Gaussian depends on the system and its width plays a role in the thermodynamic fragility. The model predicts the possibility of first-order phase transitions for fragile liquids. The analysis of laboratory data for toluene and o-terphenyl indicates that fragile liquids resolve the Kauzmann paradox by a first-order transition from supercooled liquid to ideal-glass state at a temperature between Tg and Kauzmann temperature extrapolated from experimental data. We stress the importance of the temperature dependence of the energy landscape, predicted by the fluctuation-dissipation theorem, in analyzing the liquid thermodynamics.

© 2005 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. MODEL REPRESENTATIONS IN REAL SPACE AND CONFIGURATION SPACE (ENERGY LANDSCAPE)
  3. LIQUID–LIQUID (GLASS) FIRST-ORDER PHASE TRANSITION
  4. COMPARISON TO SIMULATIONS
  5. EXPERIMENTAL CONFIGURATIONAL ENTROPIES AND THE KAUZMANN TEMPERATURE
  6. CONCLUDING REMARKS

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KEYWORDS and PACS

Keywords

organic compounds, glass transition, ground states, excited states, specific heat, Lennard-Jones potential, liquid theory, entropy, supercooling

PACS

  • 64.70.P-

    Glass transitions of specific systems

  • 64.70.Q-

    Theory and modeling of the glass transition

  • 65.20.-w

    Thermal properties of liquids

  • 61.20.-p

    Structure of liquids

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.1949211

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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