The state-to-state-to-state model for direct chemical reactions: application to D+H2-->HD+H.
The state-to-state-to-state model for direct chemical reactions: application to D+H2-->HD+H.
复制标题
直接化学反应的状态到状态到状态模型：应用于D H2-->HD H。
DOI：
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发表时间：
2006
影响因子：
4.4
通讯作者：
R. T. Skodje
中科院分区：
文献类型：
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作者：
M. Gustafsson;R. T. Skodje
本文提出了一个简单的理论模型来预测直接化学反应的态-态动力学。从过渡态理论的传统思想的启发，表达式推导出的反应性S矩阵，可以使用本地过渡态动力学计算。关键近似涉及使用量子瓶颈态来表示在过渡态附近发生的近可分离动力学。的S矩阵的显式表达式得到使用弗兰克-康登处理的碰撞复杂的内部状态之间的非弹性耦合。结果表明，D+H（2）反应的各种初始反应物态的能量阈值都可以用我们的理论来理解。具体而言，试剂状态的螺旋度被发现直接与量子瓶颈状态的对称性相关，因此具有非常不同的阈值。此外，发现D+H（2）的转动产物态分布与通过量子瓶颈态的干涉路径有关。
A simple theoretical model is developed to predict the state-to-state dynamics of direct chemical reactions. Motivated by traditional ideas from transition state theory, expressions are derived for the reactive S matrix that may be computed using the local transition state dynamics. The key approximation involves the use of quantum bottleneck states to represent the near separable dynamics taking place near the transition state. Explicit expressions for the S matrix are obtained using a Franck-Condon treatment for the inelastic coupling between internal states of the collision complex. It is demonstrated that the energetic thresholds for various initial reagent states of the D+H(2) reaction can be understood in terms of our theory. Specifically, the helicity of the reagent states are found to correlate directly to the symmetry of the quantum bottleneck states, which thus possess very different thresholds. Furthermore, the rotational product state distributions for D+H(2) are found to be associated with interfering pathways through the quantum bottleneck states.