Statistical Computation of Reaction Probabilities
Statistical Computation of Reaction Probabilities
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反应概率的统计计算
DOI：
10.1063/1.1744471
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发表时间：
1958
期刊：
影响因子：
--
通讯作者：
J. Mazur
中科院分区：
文献类型：
--
作者：
F. T. Wall;L. Hiller;J. Mazur
在高速电子数字计算机上进行了计算，以统计地确定一个简单化学反应的跃迁概率。利用共线系统H+H2势能的London - Eyring - Polanyi形式，我们求解了该系统在多种条件下的经典运动方程。研究了有初始分子振动和无初始分子振动时氢原子与氢分子的碰撞作为总动能的函数。通过对足够多的不同初始条件进行大量计算，我们获得了系统的平均行为，我们认为这提供了一个令人满意的近似量子力学平均。结果表明，当能量略高于活化能时，反应概率最大。此外，观察到，如果分子开始振动，只有一部分振动能量可用于减少kin。
Calculations have been carried out on a high‐speed electronic digital computer to determine statistically the transition probability for a simple chemical reaction. Using the London‐Eyring‐Polanyi form for the potential energy of the colinear system, H+H2, we have solved the classical equations of motion for the system under a great variety of conditions. Collisions of a hydrogen atom and a hydrogen molecule, with and without initial molecular vibration, were studied as a function of the total kinetic energy. By carrying out numerous calculations for a sufficiently large number of different initial conditions, we obtained an average behavior of the system, which we believe provides a satisfactory approximation to the quantum mechanical average. It was found that the reaction probability was greatest when the energy was just slightly above the activation energy. Moreover, it was observed that, if the molecule was initially vibrating, only a part of the energy of vibration was available for reducing the kin...