Pick R M
IMPMC, Université P. et M. Curie et CNRS-UMR 7590, Paris (F) F-75015, France.
J Chem Phys. 2008 Sep 28;129(12):124115. doi: 10.1063/1.2969899.
Prigogine-Defay ratios and, more recently, their frequency extension have been proposed to be a measure of the number of nonmacroscopic processes involved in the relaxation dynamics of supercooled liquids. We show that the microscopic theory of the Navier-Stokes equations of those liquids provides a consistent thermodynamic framework in which all possible dynamical Prigogine-Defay ratios can be expressed in terms of the same relaxation functions and that these ratios provide less information than the microscopic theory itself. The latter shows that more than one relaxation process is certainly always involved in this relaxation dynamics, whatever is the molecular dynamics, or experimental, technique used to determine the latter.
普里戈金-德法伊比率以及最近提出的其频率扩展，被认为是衡量过冷液体弛豫动力学中所涉及的非宏观过程数量的一种度量。我们表明，这些液体的纳维-斯托克斯方程的微观理论提供了一个一致的热力学框架，在该框架中，所有可能的动力学普里戈金-德法伊比率都可以用相同的弛豫函数来表示，并且这些比率所提供的信息比微观理论本身要少。后者表明，无论用于确定弛豫动力学的分子动力学或实验技术是什么，在这种弛豫动力学中肯定总是涉及不止一个弛豫过程。
