Trygubenko Semen A, Wales David J
University Chemical Laboratories, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
J Chem Phys. 2006 Jun 21;124(23):234110. doi: 10.1063/1.2198806.
We describe an exact approach for calculating transition probabilities and waiting times in finite-state discrete-time Markov processes. All the states and the rules for transitions between them must be known in advance. We can then calculate averages over a given ensemble of paths for both additive and multiplicative properties in a nonstochastic and noniterative fashion. In particular, we can calculate the mean first-passage time between arbitrary groups of stationary points for discrete path sampling databases, and hence extract phenomenological rate constants. We present a number of examples to demonstrate the efficiency and robustness of this approach.
我们描述了一种用于计算有限状态离散时间马尔可夫过程中转移概率和等待时间的精确方法。所有状态及其之间的转移规则必须预先已知。然后,我们可以以非随机和非迭代的方式计算给定路径集合上关于加性和乘性属性的平均值。特别是,对于离散路径采样数据库,我们可以计算任意固定点组之间的平均首次通过时间,从而提取唯象速率常数。我们给出了一些例子来证明这种方法的效率和稳健性。