S-matrix decomposition, natural reaction channels, and the quantum transition state approach to reactive scattering.
S-matrix decomposition, natural reaction channels, and the quantum transition state approach to reactive scattering.
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DOI：
10.1063/1.4952478
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发表时间：
2016-05
期刊：
影响因子：
--
通讯作者：
U. Manthe;R. Ellerbrock
中科院分区：
文献类型：
--
作者：
U. Manthe;R. Ellerbrock
介绍了一种多原子反应的量子态解析分析新方法。基于s矩阵的奇异值分解，定义了能量相关的自然反应通道和自然反应概率。证明了自然反应概率等于反应概率算子[U]的特征值。Manthe和w.h. Miller， J. Chem。物理学报，1999,3411(1993)]。因此，自然反应通道可以被解释为通过反应过渡态的唯一定义途径。该分析可以有效地与基于热流本征态传播的反应散射计算相结合。与直接基于热通量特征态的分解相反，它不依赖于将反应物与生成物分离的分隔面的选择。以H + CH4→H2 + CH3反应为例，对新方法进行了说明。计算并讨论了甲基产物的不同振动态对自然反应通道的贡献以及自然反应的概率。详细研究了热流本征态与自然反应通道的关系。
A new approach for the quantum-state resolved analysis of polyatomic reactions is introduced. Based on the singular value decomposition of the S-matrix, energy-dependent natural reaction channels and natural reaction probabilities are defined. It is shown that the natural reaction probabilities are equal to the eigenvalues of the reaction probability operator [U. Manthe and W. H. Miller, J. Chem. Phys. 99, 3411 (1993)]. Consequently, the natural reaction channels can be interpreted as uniquely defined pathways through the transition state of the reaction. The analysis can efficiently be combined with reactive scattering calculations based on the propagation of thermal flux eigenstates. In contrast to a decomposition based straightforwardly on thermal flux eigenstates, it does not depend on the choice of the dividing surface separating reactants from products. The new approach is illustrated studying a prototypical example, the H + CH4 → H2 + CH3 reaction. The natural reaction probabilities and the contributions of the different vibrational states of the methyl product to the natural reaction channels are calculated and discussed. The relation between the thermal flux eigenstates and the natural reaction channels is studied in detail.