Entropy and Nonlinear Nonequilibrium Thermodynamic Relation for Heat Conducting Steady States
Entropy and Nonlinear Nonequilibrium Thermodynamic Relation for Heat Conducting Steady States
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DOI：
10.1007/s10955-010-0095-5
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发表时间：
2011-01-01
影响因子：
1.6
通讯作者：
Tasaki, Hal
中科院分区：
文献类型：
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作者：
Komatsu, Teruhisa S.;Nakagawa, Naoko;Tasaki, Hal
在将熵和热力学推广到非平衡定态的各种可能途径中，我们选择了以操作热力学和克劳修斯关系为指导的途径。在我们之前的研究中，我们推导出了NESS的扩展克劳修斯关系式，其中原始关系式中的热量被其“重整化”对应物（称为过剩热量）所取代，并且吉布斯-香农熵表达式由一个新的对称化吉布斯-香农表达式代替。在这里，我们集中在马尔可夫过程描述热传导系统，并开发一个新的方法来推导热力学关系。首先给出了推广克劳修斯关系的一个新的简单推导，并阐明了它与线性响应理论的密切关系。然后，我们推导出一个新的改进的扩展克劳修斯关系与“非线性非平衡”的贡献，这是书面的功和热之间的相关性。我们认为，“非线性非平衡”的贡献是不可避免的，是唯一确定的，一旦我们接受（非常自然的）定义的多余的热量。此外，事实证明，为了在操作上确定非平衡熵与温度差的二阶的差，可以仅使用没有非线性项的先前的克劳修斯关系，或者必须使用新的关系，这取决于操作（即，参数空间中的路径）。这种奇特的“扭曲”可能是更好地理解NESS热力学和统计力学的线索。
Among various possible routes to extend entropy and thermodynamics to nonequilibrium steady states (NESS), we take the one which is guided by operational thermodynamics and the Clausius relation. In our previous study, we derived the extended Clausius relation for NESS, where the heat in the original relation is replaced by its "renormalized" counterpart called the excess heat, and the Gibbs-Shannon expression for the entropy by a new symmetrized Gibbs-Shannon-like expression. Here we concentrate on Markov processes describing heat conducting systems, and develop a new method for deriving thermodynamic relations. We first present a new simpler derivation of the extended Clausius relation, and clarify its close relation with the linear response theory. We then derive a new improved extended Clausius relation with a "nonlinear nonequilibrium" contribution which is written as a correlation between work and heat. We argue that the "nonlinear nonequilibrium" contribution is unavoidable, and is determined uniquely once we accept the (very natural) definition of the excess heat. Moreover it turns out that to operationally determine the difference in the nonequilibrium entropy to the second order in the temperature difference, one may only use the previous Clausius relation without a nonlinear term or must use the new relation, depending on the operation (i.e., the path in the parameter space). This peculiar "twist" may be a clue to a better understanding of thermodynamics and statistical mechanics of NESS.