概率Prigogine-Defay比
Configurational Prigogine-Defay ratio
摘要：
传统上，Prigogine-Defay（PD）比涉及过冷液体与玻璃化转变时的相应玻璃之间的等压体积比热、等温压缩性和等压热膨胀系数的差异。然而，通过外推分别针对过冷液体和玻璃态测量的系数来确定这样的差异，提出了没有考虑玻璃化转变的非平衡特性的问题。在本文中，我们评估这个老问题，考虑到逐步变化的构型贡献的三个热力学系数随温度和压力的变化。应用宏观非平衡态热力学方法得到了PD比的一般形式。经典的PD比可以作为这种推广的特殊情况。在某些假设下，一个配置PD比（CPD比）可以表示在虚构的温度和虚构的压力，因此，提供了实验验证这种形式主义的可能性。值得注意的是，与先前的PD比方法不同，在这里，玻璃化转变被认为是非等仿射的。
英文摘要：
Classically, the Prigogine-Defay (PD) ratio involves differences in isobaric volumic specific heat, isothermal compressibility and isobaric thermal expansion coefficient between a super-cooled liquid and the corresponding glass at the glass transition. However, determining such differences by extrapolation of coefficients that have been measured for super-cooled liquid and glassy state, respectively, poses the problem that it does not take into account the non-equilibrium character of the glass transition. In this paper, we asses this old question by taking into account the gradual change of configurational contributions to the three thermodynamic coefficients upon varying temperature and pressure. Macroscopic non-equilibrium thermodynamics is applied to obtain a generalized form of the PD ratio. The classical PD ratio can then be taken as a particular case of this generalization. Under some assumptions, a configurational PD ratio (CPD ratio) can be expressed in terms of fictive temperature and fictive pressure what, hence, provides the possibility to experimentally verify this formalism. Noteworthy and differing from previous approaches towards the PD ratio, here, the glass transition is considered as non-isoaffine.
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