Elastic models imply that the energy expended for a flow event in ultra-viscous matter coincides with the elastic work required for deforming and re-arranging the environment of the moving entity. This is quite promising for explaining the strong non-Arrhenius behavior of dynamic quantities of fragile super-cooled liquids. We argue that the activation volume obtained from dielectric relaxation and light-scattering experiments for super-cooled liquids should scale with the Gibbs free energy of activation, with a proportionality constant determined by the isothermal bulk modulus and its pressure derivative, as described by an earlier thermodynamic elastic model. For certain super-cooled liquids the bulk compression transpiring in the local environment, as governed by the isothermal bulk modulus, play a significant role in the reorientational dynamics, with far-field density fluctuations and volume changes avoided by shear deformation.
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28 December 2011
Research Article|
December 29 2011
The role of the isothermal bulk modulus in the molecular dynamics of super-cooled liquids
Anthony N. Papathanassiou;
Anthony N. Papathanassiou
a)
1Section of Solid State Physics, Physics Department,
University of Athens
, Panepistimiopolis, GR 15684 Zografos, Athens, Greece
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Ilias Sakellis;
Ilias Sakellis
1Section of Solid State Physics, Physics Department,
University of Athens
, Panepistimiopolis, GR 15684 Zografos, Athens, Greece
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John Grammatikakis;
John Grammatikakis
1Section of Solid State Physics, Physics Department,
University of Athens
, Panepistimiopolis, GR 15684 Zografos, Athens, Greece
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C. Michael Roland
C. Michael Roland
2
Naval Research Laboratory
, Chemistry Division, Code 6120, Washington, DC 20375-5342, USA
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a)
Author to whom correspondence should be addressed. Electronic mail: antpapa@phys.uoa.gr.
J. Chem. Phys. 135, 244508 (2011)
Article history
Received:
September 26 2011
Accepted:
November 15 2011
Citation
Anthony N. Papathanassiou, Ilias Sakellis, John Grammatikakis, C. Michael Roland; The role of the isothermal bulk modulus in the molecular dynamics of super-cooled liquids. J. Chem. Phys. 28 December 2011; 135 (24): 244508. https://doi.org/10.1063/1.3666008
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