Complex‐Valued Classical Trajectories for Linear Reactive Collisions of H + H2 below the Classical Threshold
Complex‐Valued Classical Trajectories for Linear Reactive Collisions of H + H2 below the Classical Threshold
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经典阈值以下 H + H2 线性反应碰撞的复值经典轨迹
DOI：
10.1063/1.1677094
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发表时间：
1972
期刊：
影响因子：
--
通讯作者：
W. Miller
中科院分区：
文献类型：
--
作者：
T. George;W. Miller
2.最近的研究表明，对于复杂的碰撞系统(如A+BG)，如何通过相空间中经典的不可达区域直接积分运动方程，从而实现这种解析延拓。对于这样的轨迹，坐标和动量，以及时间也变得复杂：有价值，但这不会对这个经典的极限理论造成问题。经典禁忌跃迁有望发挥重要作用的一种情况是存在激活势垒的热能化学反应，即低于经典反应阈值的“隧穿”区域实际上可能主导热能动力学。H+H2反应在某种意义上被认为是最类似量子的化学反应，因此应该对任何经典或半经典的反应动力学描述提出严峻的考验。
2• Quite recently it has been shown 3 how this analytic continuation can actually be carried out for complex collision systems (such as A+ BG) by integrating the equations of motion directly through classically inaccessible regions of phase space. For such trajectories the coordinates and momenta, and the time also, become complex-: valued, but this causes no problems for this classical-limit theory. One situation in which classically forbidden transitions are expected to play an important role is that of a thermal energy chemical reaction for which there is an activation barrier; ie, the" tunneling" region below the classical threshhold for reaction may actually dominate the 4 thermal energy kinetics. The H+ H 2 reaction, expected in some sense to be the most quantum-like chemical reaction, is one that should thus provide a severe test for any classical or semiclassical description of the reaction dynamics.