Ford Ian J
Department of Physics and Astronomy and London Centre for Nanotechnology, University College London, Gower Street, London WC1E 6BT, United Kingdom.
Phys Rev E Stat Nonlin Soft Matter Phys. 2015 Nov;92(5):052142. doi: 10.1103/PhysRevE.92.052142. Epub 2015 Nov 30.
The selection of an equilibrium state by maximizing the entropy of a system, subject to certain constraints, is often powerfully motivated as an exercise in logical inference, a procedure where conclusions are reached on the basis of incomplete information. But such a framework can be more compelling if it is underpinned by dynamical arguments, and we show how this can be provided by stochastic thermodynamics, where an explicit link is made between the production of entropy and the stochastic dynamics of a system coupled to an environment. The separation of entropy production into three components allows us to select a stationary state by maximizing the change, averaged over all realizations of the motion, in the principal relaxational or nonadiabatic component, equivalent to requiring that this contribution to the entropy production should become time independent for all realizations. We show that this recovers the usual equilibrium probability density function (pdf) for a conservative system in an isothermal environment, as well as the stationary nonequilibrium pdf for a particle confined to a potential under nonisothermal conditions, and a particle subject to a constant nonconservative force under isothermal conditions. The two remaining components of entropy production account for a recently discussed thermodynamic anomaly between over- and underdamped treatments of the dynamics in the nonisothermal stationary state.
通过在某些约束条件下最大化系统的熵来选择平衡态,通常被有力地推动为一种逻辑推理练习,这是一种基于不完整信息得出结论的过程。但是,如果这种框架有动力学论据作为支撑,那么它会更有说服力,我们展示了随机热力学如何做到这一点,在随机热力学中,熵的产生与耦合到环境的系统的随机动力学之间建立了明确的联系。将熵产生分为三个部分使我们能够通过最大化运动的所有实现上平均的主要弛豫或非绝热部分的变化来选择一个稳态,这相当于要求对于所有实现,对熵产生的这一贡献应与时间无关。我们表明,这恢复了等温环境中保守系统的通常平衡概率密度函数(pdf),以及非等温条件下限制在势中的粒子和等温条件下受恒定非保守力作用的粒子的稳态非平衡pdf。熵产生的另外两个部分解释了最近讨论的非等温稳态动力学的过阻尼和欠阻尼处理之间的热力学异常。