Department of Chemistry and Joint Institute for Neutron Sciences, University of Tennessee, Knoxville, Tennessee 37996, USA.
J Chem Phys. 2013 Apr 28;138(16):164508. doi: 10.1063/1.4802771.
By combining, and modestly extending, a variety of theoretical concepts for the dynamics of liquids in the supercooled regime, we formulate a simple analytic model for the temperature and wavevector dependent collective density fluctuation relaxation time that is measurable using coherent dynamic neutron scattering. Comparison with experiments on the ionic glass-forming liquid Ca-K-NO3 in the lightly supercooled regime suggests the model captures the key physics in both the local cage and mesoscopic regimes, including the unusual wavevector dependence of the collective structural relaxation time. The model is consistent with the idea that the decoupling between diffusion and viscosity is reflected in a different temperature dependence of the collective relaxation time at intermediate wavevectors and near the main (cage) peak of the static structure factor. More generally, our analysis provides support for the ideas that decoupling information and growing dynamic length scales can be at least qualitatively deduced by analyzing the collective relaxation time as a function of temperature and wavevector, and that there is a strong link between dynamic heterogeneity phenomena at the single and many particle level. Though very simple, the model can be applied to other systems, such as molecular liquids.
通过组合和适度扩展各种超冷液体动力学的理论概念,我们提出了一个简单的分析模型,用于描述可通过相干动态中子散射测量的温度和波矢相关的集体密度涨落弛豫时间。与离子玻璃形成液体 Ca-K-NO3 在轻度过冷区的实验比较表明,该模型捕捉到了局部笼和介观区域的关键物理特性,包括集体结构弛豫时间的异常波矢依赖性。该模型与扩散和粘度之间的解耦反映在中间波矢和静态结构因子主(笼)峰附近的集体弛豫时间的不同温度依赖性的观点一致。更一般地,我们的分析为以下观点提供了支持:通过分析集体弛豫时间作为温度和波矢的函数,可以至少定性地推断出信息解耦和不断增长的动态长度尺度,并且在单粒子和多粒子水平上存在强烈的动态异质性现象联系。尽管非常简单,但该模型可以应用于其他系统,例如分子液体。