发表机构
Arizona State University（亚利桑那州立大学）
机构由 AI 辅助整理，请以论文原文为准。AI 中文总结
本文综述纳米热力学，强调希尔细分势在任意尺寸系统中确保热力学定律，并展示其在伊辛模型、吉布斯悖论及涨落关系中的新解与修正，挑战可逆动力学观点。
AI 中文摘要
纳米热力学描述了大型系统细分为小子系统平衡分布的过程。一个关键要素是希尔的细分势（E），它确保系统在任何尺寸下都遵循热力学第一定律和第二定律。在这篇综述与重新评估中，强调纳米热力学为许多测量、理论和模拟提供了新的见解。确立纳米热力学必要性的测量显示，大多数类型材料内部存在来自多个有效温度（T_i）的热力学异质性。一个需要E=0的理论结果是伊辛原始模型对有限相互作用自旋链的稳定解，这是伊辛在希尔工作之前40年无法找到的解。另一个结果是对吉布斯悖论的新解，使得半经典理想气体的熵严格可加。分子动力学模拟揭示了当局部自由度波动快于其与热浴的耦合时，标准涨落关系如何被修改，这与测量的热力学异质性一致。对类Creutz模型（由伊辛自旋与爱因斯坦振子的显式热浴耦合组成）的模拟用于研究第二定律。研究发现，最大化总熵（S_t）需要内在不可逆步骤，这为通常声称统计力学源于可逆动力学提供了反例。此外，该模型的涨落最好由爱因斯坦对玻尔兹曼关系和第二定律的逆转来描述，而非近期的涨落定理。
英文摘要
Nanothermodynamics describes the process where large systems subdivide into equilibrium distributions of small subsystems. A key ingredient is Hill's subdivision potential (E) that ensures adherence to the 1st and 2nd laws of thermodynamics in systems of any size. In this review and reassessment, it is emphasized that nanothermodynamics gives new insight into many measurements, theories, and simulations. Measurements establishing the need for nanothermodynamics show thermodynamic heterogeneity from multiple effective temperatures (T_i) inside most types of materials. One theoretical result that requires E=0 is the stable solution of Ising's original model for finite chains of interacting spins, a solution Ising could not have found 40 years before Hill's work. Another result is a novel solution to Gibbs' paradox that makes the entropy of the semiclassical ideal gas exactly extensive. Molecular dynamics simulations reveal how a standard fluctuation relation is modified when local degrees of freedom fluctuate faster than their coupling to the heat bath, consistent with the measured thermodynamic heterogeneity. Simulations of a Creutz-like model, comprised of Ising spins coupled to an explicit heat bath of Einstein oscillators, are used to study the 2nd law. It is found that maximizing the total entropy (S_t) requires an intrinsically irreversible step, providing a counterexample to the usual claim that statistical mechanics emerges from reversible dynamics. Furthermore, fluctuations of this model are best described by Einstein's reversal of Boltzmann's relation and the 2nd-law, not by recent fluctuation theorems.
Comments36 pages, 10 figures
