Nonequilibrium kinetics of the gas-phase reactions of high-velocity molecules: Description by perturbation methods and simulation by statistical methods (Q1592054)

The authors present numerical solutions of a system of kinetic Boltzmann equations for a homogeneous multicomponent mixture of reacting gases with molecules of different ``colors'' that change in the reactions. The solution is obtained by Monte Carlo method, for molecules belonging to high-velocity ``tails'' of the corresponding distribution functions related to the color change reaction. The properties of the numerical solution are compared with solutions obtained by the usual perturbation method. It is shown that for the calculation of correct solutions over a range of threshold velocities it is necessary to modify substantially the perturbation method, while the traditional approach can be used only in the range of thermal particle velocities. This is definitely established for distributions of reacting molecules over their internal degrees of freedom, and for distributions of reactant molecules participating in high-threshold reactions.