论文标题

评论“热力学不确定性关系限制非平衡波动”的评论

Comment on the perspective article "Thermodynamic uncertainty relations constrain non-equilibrium fluctuations"

论文作者

Astumian, R. Dean

论文摘要

在最近的观点文章中,霍洛维茨和金里奇讨论了使用“随机热力学”得出的热力学不确定性关系,这是一种基于称为局部详细平衡的假设的理论。作者在其“框1:局部详细平衡和随机热力学的简短入门”中研究了该理论的基础,其中提出了两个储层之间颗粒传输的动力学方案。霍洛维茨(Horowitz)和金里奇(Gingrich)达成了以一个顺序通过状态循环的概率与以相反顺序循环的概率之间的关系。这种关系在一个极为重要的问题上,即当系统通过与多个不平衡的储层接触而远离平衡时,哪些方向性。在他们的论文的原始版本中,与该比率给出的关系显然是错误的,并且与热力学的第二定律相反。基于我们的私人沟通以及我的同事和我本人最近撰写的论文,霍洛维茨和金里奇接受了纠正其框1中的错误的必要性。不幸的是,不幸的是,在做出纠正时,作者介绍了同样严重的,即使透明,错误,不那么透明,错误,并继续将其理论基于热力学不可能的想法,仅在热力学上不可能地介导了两者,仅由一个重新介绍了一个重点。在此评论中,我们说明了微观可逆性的原理如何表明,状态网络中定向循环的真正起源是动力学不对称性。这种理解对于指导分子机器和其他旨在利用运输或催化以驱动非平衡过程的设备很重要。

In a recent perspective article, Horowitz and Gingrich discuss thermodynamic uncertainty relations that have been derived using "stochastic thermodynamics", a theory based on a hypothesis known as local detailed balance. The authors examined the foundations of this theory in their "Box 1: A brief primer on local detailed balance and stochastic thermodynamics", where a kinetic scheme for transport of particles between two reservoirs is presented. Horowitz and Gingrich arrive at a relationship between the probability to cycle through the states in one order vs. the probability to cycle in the reverse order. This relation bears on the extremely important question of what governs directionality when a system is driven away from equilibrium by contact with multiple reservoirs that are not in equilibrium with one another. In the original version of their paper the relation given for this ratio was obviously wrong and contrary to the second law of thermodynamics. Based on our private communications and on the recent paper authored by my colleagues and myself, Horowitz and Gingrich accepted the necessity of correcting the error in their Box 1. Unfortunately, in making the correction, the authors introduced an equally serious, if less transparent, mistake, and continue to base their theory on the thermodynamically impossible idea that transitions are mediated by only one of the two reservoirs. In this comment we illustrate how the principle of microscopic reversibility reveals that the true origin of directional cycling amongst a network of states is kinetic asymmetry. This understanding is important in guiding synthesis of molecular machines and other devices designed to exploit transport or catalysis to drive non-equilibrium processes.

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