State-to-state reaction probabilities within the quantum transition state framework.
State-to-state reaction probabilities within the quantum transition state framework.
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DOI：
10.1063/1.3684631
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发表时间：
2012-02
期刊：
影响因子：
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通讯作者：
R. Welsch;F. Huarte-Larrañaga;U. Manthe
中科院分区：
文献类型：
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作者：
R. Welsch;F. Huarte-Larrañaga;U. Manthe
在量子过渡态概念下，利用通量关联函数和波包传播，利用多组态含时Hartree方法，可以有效地计算多原子反应的反应速率和初始态选择反应几率的严格量子动力学计算。文中给出了将这种方法推广到计算状态对状态反应几率的解析公式和数值格式。推导出的公式便于使用三种不同的分割面：位于乘积和反应物渐近区域的两个分割面有助于全态分辨，而位于过渡态区域的第三个分割面可以用来定义额外的通量算符。相应的热流算符的本征态则对应于被激活的络合物的振动态。将这些态变换到反应物和产物坐标，并将它们传播到各自的渐近区域，就可以得到完整的散射矩阵。为了说明新的方法，测试计算研究了当J=0时D+H(2)(ν，j)→HD(ν‘，j’)+H反应。
Rigorous quantum dynamics calculations of reaction rates and initial state-selected reaction probabilities of polyatomic reactions can be efficiently performed within the quantum transition state concept employing flux correlation functions and wave packet propagation utilizing the multi-configurational time-dependent Hartree approach. Here, analytical formulas and a numerical scheme extending this approach to the calculation of state-to-state reaction probabilities are presented. The formulas derived facilitate the use of three different dividing surfaces: two dividing surfaces located in the product and reactant asymptotic region facilitate full state resolution while a third dividing surface placed in the transition state region can be used to define an additional flux operator. The eigenstates of the corresponding thermal flux operator then correspond to vibrational states of the activated complex. Transforming these states to reactant and product coordinates and propagating them into the respective asymptotic region, the full scattering matrix can be obtained. To illustrate the new approach, test calculations study the D + H(2)(ν, j) → HD(ν', j') + H reaction for J = 0.