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振动动力学与弛豫的热力学标度

Thermodynamic scaling of vibrational dynamics and relaxation.

作者信息

Puosi F, Chulkin O, Bernini S, Capaccioli S, Leporini D

机构信息

Dipartimento di Fisica "Enrico Fermi," Università di Pisa, Largo B. Pontecorvo 3, I-56127 Pisa, Italy.

出版信息

J Chem Phys. 2016 Dec 21;145(23):234904. doi: 10.1063/1.4971297.

Abstract

We investigate by thorough molecular dynamics simulations the thermodynamic scaling (TS) of a polymer melt. Two distinct models, with strong and weak virial-energy correlations, are considered. Both evidence the joint TS with the same characteristic exponent γ of the fast mobility-the mean square amplitude of the picosecond rattling motion inside the cage-and the much slower structural relaxation and chain reorientation. If the cage effect is appreciable, the TS master curves of the fast mobility are nearly linear, grouping in a bundle of approximately concurrent lines for different fragilities. An expression of the TS master curve of the structural relaxation with one adjustable parameter less than the available three-parameter alternatives is derived. The novel expression fits well with the experimental TS master curves of thirty-four glassformers and, in particular, their slope at the glass transition, i.e., the isochoric fragility. For the glassformer OTP, the isochoric fragility allows to satisfactorily predict the TS master curve of the fast mobility with no adjustments.

摘要

我们通过全面的分子动力学模拟研究了聚合物熔体的热力学标度(TS)。考虑了两种不同的模型,它们具有强和弱的维里能相关性。两者都证明了快速迁移率(笼内皮秒级晃动运动的均方振幅)与慢得多的结构弛豫和链重排具有相同特征指数γ的联合TS。如果笼效应显著,快速迁移率的TS主曲线几乎是线性的,对于不同的脆性,它们聚集在一束近似平行的线上。推导了结构弛豫的TS主曲线的表达式,该表达式比现有的三参数表达式少一个可调参数。这个新表达式与34种玻璃形成体的实验TS主曲线拟合良好,特别是它们在玻璃化转变处的斜率,即等容脆性。对于玻璃形成体OTP,等容脆性能够在不进行调整的情况下令人满意地预测快速迁移率的TS主曲线。

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