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内能、基本热力学关系与吉布斯系综理论作为统计计数的涌现规律

Internal Energy, Fundamental Thermodynamic Relation, and Gibbs' Ensemble Theory as Emergent Laws of Statistical Counting.

作者信息

Qian Hong

机构信息

Department of Applied Mathematics, University of Washington, Seattle, WA 98195-3925, USA.

出版信息

Entropy (Basel). 2024 Dec 13;26(12):1091. doi: 10.3390/e26121091.

Abstract

Statistical counting is the holographic observable to a statistical dynamics with finite states under independent and identically distributed sampling. Entropy provides the infinitesimal probability for an observed empirical frequency ν^ with respect to a probability prior p, when ν^≠p as N→∞. Following Callen's postulate and through Legendre-Fenchel transform, without help from mechanics, we show that an internal energy u emerges; it provides a linear representation of real-valued observables with full or partial information. Gibbs' fundamental thermodynamic relation and theory of ensembles follow mathematically. u is to ν^ what chemical potential μ is to particle number in Gibbs' chemical thermodynamics, what β=T-1 is to internal energy in classical thermodynamics, and what ω is to in Fourier analysis.

摘要

统计计数是在独立同分布采样下有限状态统计动力学的全息可观测量。当(N\to\infty)且(\hat{\nu}\neq p)时,熵为相对于概率先验(p)的观测经验频率(\hat{\nu})提供无穷小概率。遵循卡伦假设并通过勒让德 - 芬切尔变换,无需力学帮助,我们证明出现了内能(u);它为具有全部或部分信息的实值可观测量提供线性表示。吉布斯基本热力学关系和系综理论在数学上随之而来。在吉布斯化学热力学中,(u)之于(\hat{\nu})犹如化学势(\mu)之于粒子数;在经典热力学中,(\beta = T^{-1})之于内能;在傅里叶分析中,(\omega)之于[此处原文缺失相关内容]。

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本文引用的文献

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