A simple kinetic theory model of reactive collisions of rigid nonspherical molecules
A simple kinetic theory model of reactive collisions of rigid nonspherical molecules
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刚性非球形分子反应碰撞的简单动力学理论模型
DOI：
10.1063/1.448320
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发表时间：
1985
期刊：
影响因子：
--
通讯作者：
R. Bernstein
中科院分区：
文献类型：
--
作者：
G. T. Evans;Richard S. C. She;R. Bernstein
霍夫曼（1969）提出的关于刚性凸分子稀气体的经典动力学理论，现在被应用于计算一般硅藻-硅藻反应的双分子速率系数、能量依赖的反应截面σR(E)和取向依赖的微分截面。该理论包含了碰撞分子的角动量和凸形状，以及势垒高度对相互方向的依赖。考虑了几种简单的碰撞系统，包括两个反应性椭球分子的碰撞系统。对于原子-硅藻散射，发现在阈值后区域（E≥E0）， σR(E)在E−E0中有二次项和高阶项，但没有线性项。像σR一样，微分截面敏感地依赖于碰撞分子的形状，以及依赖于角度的阈值能量。对于近球面的情况，我们得到了一个简单的公式，它明确地显示了交叉角的依赖关系。
The classical kinetic theory for dilute gases of rigid convex molecules, as developed by Hoffman (1969), is now applied to the calculation on the bimolecular rate coefficient, the energy‐dependent reaction cross section σR(E), and the orientation‐dependent differential cross section, for general diatom–diatom reactions. Incorporated in the theory are the angular momentum and the convex shape of the colliding molecules, as well as the dependence of the barrier height upon mutual orientation. Several simple collision systems are considered, including that of two reactive ellipsoidal molecules. For atom–diatom scattering, it is found that, in the post‐threshold region (E≳E0), σR(E) has quadratic and higher‐order terms in E−E0 but no linear term. Like σR, the differential cross section depends sensitively upon the shape of the colliding molecules, as well as upon the angle‐dependent threshold energy. For the near‐spherical case, one obtains simple formulas that display explicitly the dependence of the cross s...