Gillespie Daniel T
Dan T. Gillespie Consulting, 30504 Cordoba Pl., Castaic, California 91384, USA.
J Phys Chem B. 2009 Feb 12;113(6):1640-4. doi: 10.1021/jp806431b.
An analysis is presented of the approximating assumptions that underlie a recently proposed derivation of the traditional deterministic reaction rate equation from a discrete-stochastic formulation of chemical kinetics. It is shown that if the system is close enough to the thermodynamic limit, in which the molecular populations and the containing volume all approach infinity in such a way that the molecular concentrations remain finite, then the required approximating assumptions will be justified for practically all spatially homogeneous systems that one is likely to encounter.
本文对一些近似假设进行了分析，这些假设构成了最近从化学动力学的离散随机公式推导传统确定性反应速率方程的基础。结果表明，如果系统足够接近热力学极限，即分子总数和容器体积都以分子浓度保持有限的方式趋近于无穷大，那么对于几乎所有可能遇到的空间均匀系统，所需的近似假设都是合理的。
