Spatially Heterogeneous Dynamics in the Density Scaling Regime: Time and Length Scales of Molecular Dynamics near the Glass Transition

被引:13
|
作者
Grzybowski, A. [1 ]
Koperwas, K. [1 ]
Kolodziejczyk, K. [1 ]
Grzybowska, K. [1 ]
Paluch, M. [1 ]
机构
[1] Univ Silesia, Inst Phys, PL-40007 Katowice, Poland
来源
关键词
CONFIGURATIONAL ENTROPY; STRUCTURAL RELAXATION; POLYVINYL ACETATE); BETA-RELAXATION; FORMING LIQUIDS; TEMPERATURE; PRESSURE; VOLUME; PRIGOGINE; POLYMERS;
D O I
10.1021/jz402060x
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A fundamental problem of glass transition physics is to find a proper relation between length and time scales of molecular dynamics near the glass transition. Until now, this relation has been usually expected as a single variable function, for instance, as a consequence of the suggested direct relation between the structural relaxation time tau and the correlation volume defined by the maximum of the four-point correlation function chi(max)(4). Based on high pressure data analyses, we show that it is not the case, because chi(max)(4) evaluated from its estimate based on the enthalpy fluctuations cannot be, in general, a single variable function of tau. For a wide class of real and model supercooled liquids, the molecular dynamics of which obeys a density scaling law at least to a good approximation, we argue that the important relation between the length and time scales that characterize molecular motions near the glass transition is controlled by a density factor, the exponent of which is a measure of the observed decoupling between tau and chi(max)(4). This finding substantially changes our understanding of molecular dynamics near the glass transition.
引用
收藏
页码:4273 / 4278
页数:6
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