On the origins of approximations for stochastic chemical kinetics.
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.
Haseltine
Eric L
EL
Division of Chemistry and Chemical Engineering 210-41, California Institute of Technology, Pasadena, California 91125, USA.
Rawlings
James B
JB
D000465:Algorithms; D002627:Chemistry, Physical / Q000379:methods*; D003198:Computer Simulation; D007700:Kinetics; D008390:Markov Chains; D008956:Models, Chemical; D015233:Models, Statistical; D011336:Probability; D013269:Stochastic Processes