介观统计热力学的理论与实验进展

Hai-Tao Quan, Hui Dong, Chang-Pu Sun
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摘要

热力学对于只有有限自由度的微观小系统仍然成立吗?温度、熵、做功、传热、等温过程和卡诺循环等概念还有效吗?与传统的宏观热力学相比,小系统热力学理论是否需要修改或补充?以单粒子系统为例,研究了热力学概念和定律在小系统中的适用性。我们已经发现热力学定律在小系统的总体平均水平上仍然成立。在考虑麦克斯韦妖的信息擦除后,热力学第二定律没有被违反。此外,“小型系统”带来了一些新功能。热力学量的波动变得突出。在任何远离平衡态的过程中,热力学量的分布函数都满足某些严格建立的恒等式。这些恒等式被称为涨落定理。热力学第二定律可以从它们推导出来。因此,涨落定理可以看作是热力学第二定律的升级。它们使物理学家能够通过测量与非平衡过程(如功分布)相关的物理量来获得平衡特性(如自由能差)。此外,尽管量子热机具有一些明显的量子特征,但其性能并不优于经典热机。在小系统中引入运动方程,使热力学和力学的关系更加紧密。物理学家可以从热力学第一原理出发,研究非平衡过程中的能量耗散,优化热机的功率和效率。这些发现丰富了热力学理论的内容,为建立非平衡态热力学的一般框架提供了新的思路。
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Theoretical and experimental progress of mesoscopic statistical thermodynamics
Does thermodynamics still hold true for mecroscopic small systems with only limited degrees of freedom? Do concepts such as temperature, entropy, work done, heat transfer, isothermal processes, and the Carnot cycle remain valid? Does the thermodynamic theory for small systems need modifying or supplementing compared with traditional thermodynamics applicable to macroscopic systems? Taking a single-particle system for example, we investigate the applicability of thermodynamic concepts and laws in small systems. We have found that thermodynamic laws still hold true in small systems at an ensemble-averaged level. After considering the information erasure of the Maxwell's demon, the second law of thermodynamics is not violated. Additionally, 'small systems' bring some new features. Fluctuations in thermodynamic quantities become prominent. In any process far from equilibrium, the distribution functions of thermodynamic quantities satisfy certain rigorously established identities. These identities are known as fluctuation theorems. The second law of thermodynamics can be derived from them. Therefore, fluctuation theorems can be considered an upgradation to the second law of thermodynamics. They enable physicists to obtain equilibrium properties (e.g. free energy difference) by measuring physical quantities associated with non-equilibrium processes (e.g. work distributions). Furthermore, despite some distinct quantum features, the performance of quantum heat engine does not outperform that of classical heat engine. The introduction of motion equations into small system makes the relationship between thermodynamics and mechanics closer than before. Physicists can study energy dissipation in non-equilibrium process and optimize the power and efficiency of heat engine from the first principle. These findings enrich the content of thermodynamic theory and provide new ideas for establishing a general framework for non-equilibrium thermodynamics.
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