Global Reaction Rates from Local Cluster Distributions

Abstract

ABSTRACTThe well-known model reactions A+A⇢0 and A+B⇢0 are examined in terms of the microscopic geometric arrangements of the reactants that may possibly lead to reaction. The reaction takes place only upon physical short-ranged collision of the reactants. Different dimensionalities are examined, and for each one of these arrangements all possible arrangements of the reactants are enumarated. Then, the frequency (probability) is taken into account, and an overall rate is formed. This rate is monitored in the course of the reaction in the simulation calculation and compared to the overall rate derived the traditional way from the densities. These two rates agree very well. Finally, the pair correlation functions are calculated as a function of time from the simulation data, and they are also in good agreement with previous studies.