Brandão Fernando, Horodecki Michał, Ng Nelly, Oppenheim Jonathan, Wehner Stephanie
Department of Computer Science, University College London, London WC1E 6BT, United Kingdom;
Instytut Fizyki Teoretycznej i Astrofizyki, University of Gdansk, 80-952 Gdansk, Poland;
Proc Natl Acad Sci U S A. 2015 Mar 17;112(11):3275-9. doi: 10.1073/pnas.1411728112. Epub 2015 Feb 9.
The second law of thermodynamics places constraints on state transformations. It applies to systems composed of many particles, however, we are seeing that one can formulate laws of thermodynamics when only a small number of particles are interacting with a heat bath. Is there a second law of thermodynamics in this regime? Here, we find that for processes which are approximately cyclic, the second law for microscopic systems takes on a different form compared to the macroscopic scale, imposing not just one constraint on state transformations, but an entire family of constraints. We find a family of free energies which generalize the traditional one, and show that they can never increase. The ordinary second law relates to one of these, with the remainder imposing additional constraints on thermodynamic transitions. We find three regimes which determine which family of second laws govern state transitions, depending on how cyclic the process is. In one regime one can cause an apparent violation of the usual second law, through a process of embezzling work from a large system which remains arbitrarily close to its original state. These second laws are relevant for small systems, and also apply to individual macroscopic systems interacting via long-range interactions. By making precise the definition of thermal operations, the laws of thermodynamics are unified in this framework, with the first law defining the class of operations, the zeroth law emerging as an equivalence relation between thermal states, and the remaining laws being monotonicity of our generalized free energies.
热力学第二定律对状态转变施加了限制。它适用于由许多粒子组成的系统,然而,我们发现当只有少量粒子与热库相互作用时,也可以制定热力学定律。在这种情况下是否存在热力学第二定律呢?在这里,我们发现对于近似循环的过程,微观系统的第二定律与宏观尺度相比呈现出不同的形式,它不仅对状态转变施加一个限制,而是施加一整个系列的限制。我们发现了一族自由能,它们推广了传统的自由能,并表明它们永远不会增加。普通的第二定律涉及其中之一,其余的则对热力学转变施加额外的限制。我们发现有三种情况,这取决于过程的循环程度,决定了哪一族第二定律支配状态转变。在一种情况下,可以通过从一个始终任意接近其原始状态的大系统中挪用功的过程,导致对通常第二定律的明显违反。这些第二定律与小系统相关,也适用于通过长程相互作用相互作用的单个宏观系统。通过精确热操作的定义,热力学定律在这个框架中得到统一,第一定律定义了操作的类别,第零定律作为热状态之间的等价关系出现,其余定律则是我们广义自由能的单调性。