Bell Ian H, Galliero Guillaume, Delage-Santacreu Stéphanie, Costigliola Lorenzo
Applied Chemicals and Materials Division, National Institute of Standards and Technology, Boulder, Colorado 80305, USA.
Universite de Pau et des Pays de l'Adour, e2s UPPA, TOTAL, CNRS, LFCR, UMR 5150, Laboratoire des fluides complexes et leurs reservoirs, Pau, France.
J Chem Phys. 2020 May 21;152(19):191102. doi: 10.1063/1.5143854.
In this work, we propose a generic and simple definition of a line separating gas-like and liquid-like fluid behaviors from the standpoint of shear viscosity. This definition is valid even for fluids such as the hard sphere and the inverse power law that exhibit a unique fluid phase. We argue that this line is defined by the location of the minimum of the macroscopically scaled viscosity when plotted as a function of the excess entropy, which differs from the popular Widom lines. For hard sphere, Lennard-Jones, and inverse-power-law fluids, such a line is located at an excess entropy approximately equal to -2/3 times Boltzmann's constant and corresponds to points in the thermodynamic phase diagram for which the kinetic contribution to viscosity is approximately half of the total viscosity. For flexible Lennard-Jones chains, the excess entropy at the minimum is a linear function of the chain length. This definition opens a straightforward route to classify the dynamical behavior of fluids from a single thermodynamic quantity obtainable from high-accuracy thermodynamic models.
在这项工作中,我们从剪切粘度的角度提出了一个通用且简单的定义,用于区分类气态和类液态流体行为。即使对于诸如硬球和逆幂律等呈现单一流体相的流体,该定义也是有效的。我们认为这条线是由宏观尺度粘度作为过量熵的函数绘制时的最小值位置所定义的,这与常见的维德曼线不同。对于硬球、 Lennard-Jones 和逆幂律流体,这样一条线位于过量熵约等于玻尔兹曼常数的 -2/3 倍处,并且对应于热力学相图中动力学对粘度的贡献约为总粘度一半的点。对于柔性 Lennard-Jones 链,最小值处的过量熵是链长的线性函数。这个定义为从高精度热力学模型可获得的单个热力学量来分类流体的动力学行为开辟了一条直接的途径。