Recently, a combined study of high-resolution molecular crossed beam experiment and accurate full-dimensional time-dependent theory, including full spin–orbit characteristics on the effect of electronic spin and orbital angular momenta in the F + HD reaction, was reported by some of us, focusing on the partial wave resonance phenomenon (Science 2021, 371, 936–940). It revealed that the time-dependent theory could explain all of the details observed in the high-resolution experiment. Here, we develop two time-independent close-coupling methods using hyperspherical coordinates, including the two-state model, where only a part of the spin–orbit characteristics is considered, and the six-state model, where the full spin–orbit characteristics is considered. With these two newly developed theoretical models and the adiabatic theoretical model, the detailed reaction dynamics of the F + HD (v = 0, j = 0) reaction and the Cl + H₂ (v = 0, j = 0) reaction are investigated and compared. Some of the results are compared with the time-dependent quantum wave packet theory and the experimental observations, and good agreements have been obtained, which suggests the validity of the pure-procession approximation in the six-state model using different theoretical methods. This work demonstrates the ability of the reactive scattering theory including full spin–orbit characteristics for describing the reactions of a halogen atom plus hydrogen molecule and its isotopologues.

中文翻译：

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使用包括（全）自旋轨道特征的超球坐标开发 Cl + H2/F + HD 反应的时间无关方法

最近，一些人报道了高分辨率分子交叉束实验和精确全维时间相关理论的联合研究，包括全自旋轨道特性对F + HD反应中电子自旋和轨道角动量的影响。我们，重点关注部分波共振现象（Science 2021, 371, 936–940）。它表明，时间相关理论可以解释高分辨率实验中观察到的所有细节。在这里，我们使用超球面坐标开发了两种与时间无关的紧密耦合方法，包括仅考虑部分自旋轨道特性的二态模型和考虑完整自旋轨道特性的六态模型被认为。利用这两个新发展的理论模型和绝热理论模型，研究了F + HD ( v = 0, j = 0) 反应和Cl + H ₂ ( v = 0, j = 0) 反应的详细反应动力学并进行了比较。一些结果与时间相关的量子波包理论和实验观察进行了比较，得到了很好的一致性，这表明使用不同理论方法在六态模型中纯过程近似的有效性。这项工作展示了反应散射理论的能力，包括描述卤素原子加氢分子及其同位素异体反应的全自旋轨道特征。