弛豫时间和剩余熵的非平衡态方法
Hierarchy of Relaxation times and Residual Entropy: A Nonequilibrium Approach
摘要：
我们考虑非平衡（NEQ）状态，如过冷液体和玻璃，用内部变量描述。我们对后者进行分类的状态依赖的层次结构的弛豫时间，以评估其相关性的不可逆的贡献。在给定观测时间τ obs的条件下，我们确定了弛豫时间窗口，该窗口将内变量分为活动组和非活动组，前者在NEQ热力学中起着核心作用。使用这个热力学，我们确定（i）一个约束的NEQ熵和剩余熵，和（ii）的性质的等温松弛的熵和焓按照第二定律。一个违反第二定律的理论，如熵损失观点，如果我们要求它与实验一致，那么它就是内部不一致的。不活动的内部变量在确定系统的温度T（t）、压力P（t）时仍然起间接作用，温度T（t）、压力P（t）偏离它们的外部值。
英文摘要：
We consider nonequilibrium (NEQ) states such as supercooled liquids and glasses that are described with use of internal variables. We classify the latter by state-dependent hierarchy of relaxation times to assess their relevance for irreversible contributions. Given an observation time τ_{obs}, we determine the window of relaxation times that divide the internal variables into active and inactive groups, the former playing a central role in the NEQ thermodynamics. Using this thermodynamics, we determine (i) a bound on the NEQ entropy and on the residual entropy, and (ii) the nature of isothermal relaxation of the entropy and the enthalpy in accordance with the second law. A theory that violates the second law such as the entropy loss view is shown to be internally inconsistent if we require it to be consistent with experiments. The inactive internal variables still play an indirect role in determining the temperature T(t), the pressure P(t), of the system, which deviate from their external values.
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