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Dynamics of glass-forming liquids. XVIII. Does entropy control structural relaxation times?

作者信息

Samanta Subarna, Richert Ranko

机构信息

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

出版信息

J Chem Phys. 2015 Jan 28;142(4):044504. doi: 10.1063/1.4906191.

DOI:10.1063/1.4906191
PMID:25637992
Abstract

We study the dielectric dynamics of viscous glycerol in the presence of a large bias field. Apart from dielectric saturation and polarization anisotropy, we observe that the steady state structural relaxation time is longer by 2.7% in the presence of a 225 kV/cm dc-field relative to the linear response counterpart, equivalent to a field induced glass transition (Tg) shift of +84 mK. This result compares favorably with the 3.0% time constant increase predicted on the basis of a recent report [G. P. Johari, J. Chem. Phys. 138, 154503 (2013)], where the field induced reduction of the configurational entropy translates into slower dynamics by virtue of the Adam-Gibbs relation. Other models of field dependent glass transition temperatures are also discussed. Similar to observations related to the electro-optical Kerr effect, the rise time of the field induced effect is much longer than its collapse when the field is removed again. The orientational relaxation time of the plastic crystal cyclo-octanol is more sensitive to a bias field, showing a 13.5% increase at a field of 150 kV/cm, equivalent to an increase of Tg by 0.58 K.

摘要

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