DOI: 10.1063/1.3119641. On dynamic heterogeneity in supercooled liquids

On dynamic heterogeneity in supercooled liquids

10.1063/1.3119641

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

A simplified molecular theory for the dynamics of liquids near the glass transition temperature Tg is developed and compared with experimental viscosity and diffusion behavior. Its basis is the spatial fluctuations of local density, a property that depends on isothermal compressibility and thus occurs naturally in all liquids at equilibrium. Instantaneous liquid structure is approximated by randomly distributed arrays of two domains having either higher or lower density than the average. The time dependence of fluctuations is represented by a sequence of such structures, each having a lifetime that varies with the macroscopic density. The dynamic environment of a molecule within a domain (slow or fast) depends on the density of its domain (high or low). Translational diffusion and orientational relaxation depend on different averages of the slow and fast domain contributions and lead, on approaching Tg, to a progressive departure from the Stoke–Einstein relationship. Predictions are made using macroscopic viscosity-density relationships within the individual domains. They depend only on the choice of domain size, which, according to this formulation, is insensitive to temperature. The data for three well-studied nonpolymeric liquids were found to be in reasonable accord with NMR assessments of domain size.

Bibliography

Graessley, W. W. (2009). On dynamic heterogeneity in supercooled liquids. The Journal of Chemical Physics, 130(16).

Authors 1

William W. Graessley (first)

References 47 Referenced 8

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Dates

Type	When
Created	16 years, 4 months ago (April 22, 2009, 6:28 p.m.)
Deposited	1 year, 5 months ago (March 12, 2024, 4:56 p.m.)
Indexed	4 weeks ago (July 30, 2025, 6:52 a.m.)
Issued	16 years, 4 months ago (April 22, 2009)
Published	16 years, 4 months ago (April 22, 2009)
Published Online	16 years, 4 months ago (April 22, 2009)
Published Print	16 years, 3 months ago (April 28, 2009)

Funders 0

None

BibTeX

@article{Graessley_2009, title={On dynamic heterogeneity in supercooled liquids}, volume={130}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.3119641}, DOI={10.1063/1.3119641}, number={16}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Graessley, William W.}, year={2009}, month=apr }

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  "subject": [],
  "published-other": {
    "date-parts": [
      [
        2009,
        4,
        28
      ]
    ]
  },
  "published": {
    "date-parts": [
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        4,
        22
      ]
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  },
  "article-number": "164502"
}