非平衡界面热力学对至关重要的生物,物理,和工业规模的运输过程。这里,我们讨论了多相多组分界面的局部平衡理论,该理论建立在吉布斯首先引入的“尖锐”界面概念的基础上,允许描述非平衡界面过程,例如在蒸发中产生的过程,冷凝,吸附,等。通过要求热力学对分隔面的精确位置不敏感,人们可以确定局部平衡的条件,并开发出测量界面上密集变量值的方法。然后我们使用广泛的,高精度非平衡分子动力学(NEMD)模拟验证理论,建立局部平衡假设的有效性。特别是,我们证明了平衡状态方程在不平衡状态下也是有效的,可用于确定与Clapeyron和Gibbs吸附方程的非平衡概括一致的界面温度和化学势。我们也展示,例如,That,远离平衡,温度或化学电位差不需要在界面上是均匀的,而是可以表现出明显的不连续性。然而,即使在这种情况下,我们证明了局部均衡假设及其含义仍然有效。这些结果为研究或重新研究各种界面传输现象提供了热力学基础和计算工具。
Nonequilibrium interfacial thermodynamics has important implications for crucial biological, physical, and industrial-scale transport processes. Here, we discuss a theory of local equilibrium for multiphase multicomponent interfaces that builds upon the \"sharp\" interface concept first introduced by Gibbs, allowing for a description of nonequilibrium interfacial processes such as those arising in evaporation, condensation, adsorption, etc. By requiring that the thermodynamics be insensitive to the precise location of the dividing surface, one can identify conditions for local equilibrium and develop methods for measuring the values of intensive variables at the interface. We then use extensive, high-precision nonequilibrium molecular dynamics (NEMD) simulations to verify the theory and establish the validity of the local equilibrium hypothesis. In particular, we demonstrate that equilibrium equations of state are also valid out of equilibrium, and can be used to determine interfacial temperature and chemical potential(s) that are consistent with nonequilibrium generalizations of the Clapeyron and Gibbs adsorption equations. We also show, for example, that, far from equilibrium, temperature or chemical potential differences need not be uniform across an interface and may instead exhibit pronounced discontinuities. However, even in these circumstances, we demonstrate that the local equilibrium hypothesis and its implications remain valid. These results provide a thermodynamic foundation and computational tools for studying or revisiting a wide variety of interfacial transport phenomena.