多通道多位井速率常数的计算.ppt

化学反应速率理论 碰撞理论（经典碰撞理论，轨线法，量子散射理论） 过渡状态理论（传统过渡状态理论，变分过渡状态理论） 过渡状态理论的基本假设 玻恩-奥本海默近似 反应物微观状态保持玻尔兹曼分布 不返回假定 运动分离假定 化学反应速率常数的计算 正则系综速率常数的计算 传统过渡态理论 正则变分过渡态理论 隧道穿透系数的计算 * * 多通道多位井速率常数的计算 Rate Constants for Multi-Channel, Multi-Well Reactions 张绍文 北京理工大学 考虑到量子隧道效应时 微正则系综速率常数的计算 传统过渡态理论 微正则变分过渡态理论 BWK近似 Master Equation Method Why Use Master Equation Calculate pressure dependence of rate constants Calculate branching ratios of multi-channel reactions High accuracy Single Well Multi-channel Case B + C D + E F + G A Methodology A B + C E E0 Ei k(Ei) Ej Rji A B+C ni nj ni is the population of reactant molecules at energy Ei. [M] is the concentration of bath gas. Rij is the rate of collision-induced excitation from Ej to Ei of the reactant molecule on collision with a bath gas molecule (Energy transfer coefficient). k(Ei) is the microcanonical rate constant of the reaction at energy Ei Gilbert, R. G.; Smith, S. C. Theory of Unimolecular and Recombination Reactions; Blackwell: London, 1990. Klippenstein, S. J., Harding, L. B. J. Phys. Chem. 1999, 103, 9388. Diau, E. W. G, Lin M. C. J. Phys. Chem. 1995, 99, 6589. Robertson, S. H., Pilling, M. J., Baulch, D. L., Green, N. J. B. J. Phys. Chem. 1995, 99, 13452. Z: collision number per unit time, collision frequency, (time-1) Pi(E,E’): probability of energy transferred per collision, (energy-1) kuni is pressure dependent thermal rate constants Energy Transfer Rate Coefficient Pij=c(Ej)exp[-(Ej-Ei)/?], Ei Ej Exponential down model Pji f(Ei) = Pij f(Ej) f(Ei) = [?(Ei) exp(- Ei/kBT)]/Q c(E) is normalization coefficient; ? is energy transfer constant; f(E) is distribution function; ?(E) is density of state; Q is partition function. E Ei Ej Rji Microcanonical Rate Constant NGTS(E,S) is the sum of states of the Generalized Transition State (GTS). ?R(E) is the density of states of the reactant. 1. Garrett, B. C.; Truhlar, D. G.; Grev, R. S.; Magnuson, A. W. J. Phys. Chem. 1980, 84, 1370. 2. Hase, W.