Perspective: Excess-entropy scaling

被引:211
作者
Dyre, Jeppe C. [1 ]
机构
[1] Roskilde Univ, Dept Sci & Environm, IMFUFA, Glass & Time, POB 260, DK-4000 Roskilde, Denmark
关键词
SELF-DIFFUSION COEFFICIENTS; KOLMOGOROV-SINAI ENTROPY; TRANSPORT-PROPERTIES; PERTURBATION-THEORY; GLASS-TRANSITION; ENERGY LANDSCAPE; STRUCTURAL TRANSITIONS; MOLECULAR-DYNAMICS; ATOMIC TRANSPORT; SHEAR VISCOSITY;
D O I
10.1063/1.5055064
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
This article gives an overview of excess-entropy scaling, the 1977 discovery by Rosenfeld that entropy determines properties of liquids like viscosity, diffusion constant, and heat conductivity. We give examples from computer simulations confirming this intriguing connection between dynamics and thermodynamics, counterexamples, and experimental validations. Recent uses in application-related contexts are reviewed, and theories proposed for the origin of excess-entropy scaling are briefly summarized. It is shown that if two thermodynamic state points of a liquid have the same microscopic dynamics, they must have the same excess entropy. In this case, the potential-energy function exhibits a symmetry termed hidden scale invariance, stating that the ordering of the potential energies of configurations is maintained if these are scaled uniformly to a different density. This property leads to the isomorph theory, which provides a general framework for excess-entropy scaling and illuminates, in particular, why this does not apply rigorously and universally. It remains an open question whether all aspects of excess-entropy scaling and related regularities reflect hidden scale invariance in one form or other. Published by AIP Publishing.
引用
收藏
页数:21
相关论文
共 201 条
[21]   Viscosity models for pure hydrocarbons at extreme conditions: A review and comparative study [J].
Baled, Hseen O. ;
Gamwo, Isaac K. ;
Enick, Robert M. ;
McHugh, Mark A. .
FUEL, 2018, 218 :89-111
[22]   Diffusion on a rugged energy landscape with spatial correlations [J].
Banerjee, Saikat ;
Biswas, Rajib ;
Seki, Kazuhiko ;
Bagchi, Biman .
JOURNAL OF CHEMICAL PHYSICS, 2014, 141 (12)
[23]   DIRECT ENTROPY CALCULATION FROM COMPUTER-SIMULATION OF LIQUIDS [J].
BARANYAI, A ;
EVANS, DJ .
PHYSICAL REVIEW A, 1989, 40 (07) :3817-3822
[24]   WHAT IS LIQUID - UNDERSTANDING STATES OF MATTER [J].
BARKER, JA ;
HENDERSON, D .
REVIEWS OF MODERN PHYSICS, 1976, 48 (04) :587-671
[25]   Entropy scaling laws for diffusion [J].
Bastea, S .
PHYSICAL REVIEW LETTERS, 2004, 93 (19)
[26]   Thermodynamics and diffusion in size-symmetric and asymmetric dense electrolytes [J].
Bastea, Sorin .
JOURNAL OF CHEMICAL PHYSICS, 2011, 135 (08)
[27]  
Bell I. H., 2018, ARXIV180905682
[28]   Pure and Pseudo-pure Fluid Thermophysical Property Evaluation and the Open-Source Thermophysical Property Library CoolProp [J].
Bell, Ian H. ;
Wronski, Jorrit ;
Quoilin, Sylvain ;
Lemort, Vincent .
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 2014, 53 (06) :2498-2508
[29]   Reformulation of Weeks-Chandler-Andersen perturbation theory directly in terms of a hard-sphere reference system [J].
Ben-Amotz, D ;
Stell, G .
JOURNAL OF PHYSICAL CHEMISTRY B, 2004, 108 (21) :6877-6882
[30]   EXCESS ENTROPY AT GLASS TRANSFORMATION [J].
BESTUL, AB ;
CHANG, SS .
JOURNAL OF CHEMICAL PHYSICS, 1964, 40 (12) :3731-&