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平衡态与非平衡态热力学的随机方法。

Stochastic approach to equilibrium and nonequilibrium thermodynamics.

作者信息

Tomé Tânia, de Oliveira Mário J

机构信息

Instituto de Física, Universidade de São Paulo, Caixa Postal 66318 05314-970 São Paulo, São Paulo, Brazil.

出版信息

Phys Rev E Stat Nonlin Soft Matter Phys. 2015 Apr;91(4):042140. doi: 10.1103/PhysRevE.91.042140. Epub 2015 Apr 29.

Abstract

We develop the stochastic approach to thermodynamics based on stochastic dynamics, which can be discrete (master equation) and continuous (Fokker-Planck equation), and on two assumptions concerning entropy. The first is the definition of entropy itself and the second the definition of entropy production rate, which is non-negative and vanishes in thermodynamic equilibrium. Based on these assumptions, we study interacting systems with many degrees of freedom in equilibrium or out of thermodynamic equilibrium and how the macroscopic laws are derived from the stochastic dynamics. These studies include the quasiequilibrium processes; the convexity of the equilibrium surface; the monotonic time behavior of thermodynamic potentials, including entropy; the bilinear form of the entropy production rate; the Onsager coefficients and reciprocal relations; and the nonequilibrium steady states of chemical reactions.

摘要

我们基于随机动力学开发了热力学的随机方法,随机动力学可以是离散的(主方程)和连续的(福克 - 普朗克方程),并且基于关于熵的两个假设。第一个是熵本身的定义,第二个是熵产生率的定义,熵产生率是非负的且在热力学平衡中消失。基于这些假设,我们研究处于平衡或偏离热力学平衡的具有多个自由度的相互作用系统,以及宏观定律如何从随机动力学推导出来。这些研究包括准平衡过程;平衡面的凸性;热力学势(包括熵)的单调时间行为;熵产生率的双线性形式;昂萨格系数和互易关系;以及化学反应的非平衡稳态。

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