Doktorov Alexander B, Kipriyanov Alexey A
Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, Novosibirsk State University, Novosibirsk 630090, Russia.
J Chem Phys. 2014 May 14;140(18):184104. doi: 10.1063/1.4874001.
General matrix approach to the consideration of multistage geminate reactions of isolated pairs of reactants depending on reactant mobility is formulated on the basis of the concept of "effective" particles. Various elementary reactions (stages of multistage reaction including physicochemical processes of internal quantum state changes) proceeding with the participation of isolated pairs of reactants (or isolated reactants) are taken into account. Investigation has been made in terms of kinetic approach implying the derivation of general (matrix) kinetic equations for local and mean probabilities of finding any of the reaction species in the sample under study (or for local and mean concentrations). The recipes for the calculation of kinetic coefficients of the equations for mean quantities in terms of relative coordinates of reactants have been formulated in the general case of inhomogeneous reacting systems. Important specific case of homogeneous reacting systems is considered.
基于“有效”粒子的概念，制定了一种通用矩阵方法，用于考虑取决于反应物迁移率的孤立反应物对的多阶段双分子反应。考虑了各种基本反应（包括内部量子态变化的物理化学过程的多阶段反应阶段），这些反应在孤立反应物对（或孤立反应物）的参与下进行。研究采用动力学方法，即推导用于在所研究样品中找到任何反应物种的局部和平均概率（或局部和平均浓度）的通用（矩阵）动力学方程。在非均匀反应体系的一般情况下，已经制定了根据反应物相对坐标计算平均量方程动力学系数的方法。还考虑了均匀反应体系的重要特殊情况。
