Chelli Riccardo
Dipartimento di Chimica, Università di Firenze, Via della Lastruccia 3, I-50019 Sesto Fiorentino, Italy.
J Chem Phys. 2009 Feb 7;130(5):054102. doi: 10.1063/1.3067878.
Generalized forms of the Crooks fluctuation theorem are derived for non-Hamiltonian and Hamiltonian systems subject to both mechanical and thermal changes. Almost identical derivations are provided for the two cases under rather general assumptions. The basic one is that the probability distribution is a stationary solution of the Liouville equation for fixed values of mechanical control parameters applied to collective variables of the system and for fixed temperature. Generalized expressions for several nonequilibrium work relations derivable from the Crooks fluctuation theorem, such as the Jarzynski equality, path-ensemble averages for systems driven far from equilibrium, Bennett acceptance ratio, and two work-based potential of mean force estimators, are also derived. Although this list is not complete, the extension to other related work theorems is straightforward. The application of the methodology is illustrated for two representative cases, namely, for systems evolving with isochoric-isokinetic and isothermal-isobaric equations of motion.
针对受机械和热变化影响的非哈密顿系统和哈密顿系统，推导了克鲁克斯涨落定理的广义形式。在相当一般的假设下，为这两种情况提供了几乎相同的推导。基本假设是，对于应用于系统集体变量的机械控制参数的固定值以及固定温度，概率分布是刘维尔方程的平稳解。还推导了可从克鲁克斯涨落定理得出的几个非平衡功关系的广义表达式，如雅津斯基等式、远离平衡驱动系统的路径系综平均值、贝内特接受率以及两个基于功的平均力估计势。尽管此列表并不完整，但扩展到其他相关功定理很简单。针对两个代表性情况说明了该方法的应用，即对于遵循等容 - 等动力学和等温 - 等压运动方程演化的系统。
