Haseltine Eric L, Rawlings James B
Division of Chemistry and Chemical Engineering 210-41, California Institute of Technology, Pasadena, California 91125, USA.
J Chem Phys. 2005 Oct 22;123(16):164115. doi: 10.1063/1.2062048.
This paper considers the derivation of approximations for stochastic chemical kinetics governed by the discrete master equation. Here, the concepts of (1) partitioning on the basis of fast and slow reactions as opposed to fast and slow species and (2) conditional probability densities are used to derive approximate, partitioned master equations, which are Markovian in nature, from the original master equation. Under different conditions dictated by relaxation time arguments, such approximations give rise to both the equilibrium and hybrid (deterministic or Langevin equations coupled with discrete stochastic simulation) approximations previously reported. In addition, the derivation points out several weaknesses in previous justifications of both the hybrid and equilibrium systems and demonstrates the connection between the original and approximate master equations. Two simple examples illustrate situations in which these two approximate methods are applicable and demonstrate the two methods' efficiencies.
本文考虑由离散主方程所支配的随机化学动力学近似的推导。在此,(1)基于快速和慢速反应而非快速和慢速物种进行划分的概念,以及(2)条件概率密度,被用于从原始主方程推导出本质上为马尔可夫的近似划分主方程。在由弛豫时间论据所规定的不同条件下,此类近似产生了先前报道的平衡近似和混合近似(确定性或朗之万方程与离散随机模拟相结合)。此外,该推导指出了先前对混合系统和平衡系统论证中的几个弱点,并展示了原始主方程与近似主方程之间的联系。两个简单例子说明了这两种近似方法适用的情形,并展示了这两种方法的效率。