Voevodsky Institute of Chemical Kinetics and Combustion, SB RAS, 630090 Novosibirsk, Russia.
J Chem Phys. 2018 Sep 7;149(9):094102. doi: 10.1063/1.5040015.
General matrix algebraic equations for calculating rate constants of multistage diffusion-influenced reactions (involving bimolecular exchange reactions as elementary stages) in liquid solutions that proceed from different active sites in the immediate vicinity of the contact of reactants have been obtained on the basis of the kinematic approximation developed by the authors earlier. The equations make it possible to express rate constants of any multistage multisite bimolecular reaction between non-identical reactants in terms of the defined reaction constants and stationary Green functions averaged over reaction sites and completely determined by molecular motion of reactants or their molecular groups. The asymptotic behavior of these rate constants as they attain their steady-state values on completion of the transient stage is established. It is shown that it coincides with the corresponding exact time asymptote. Calculations are made with some specific two-stage (three-channel) bimolecular reactions as an example.
基于作者之前发展的运动学近似，得到了用于计算液体溶液中多步扩散影响反应（涉及双分子交换反应作为基本阶段）的速率常数的一般矩阵代数方程，这些反应从反应物接触点附近的不同活性位置进行。这些方程使得能够根据定义的反应常数和在反应位置上平均的静态格林函数来表示任意多步多位置双分子反应的速率常数，这些函数完全由反应物或其分子基团的分子运动决定。确定了这些速率常数在瞬态阶段完成后达到稳定状态值时的渐近行为。结果表明，它与相应的精确时间渐近线吻合。以某些特定的两步（三通道）双分子反应为例进行了计算。
