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中国物理学会期刊

冷分子反应碰撞的立体动力学调控:S(1D)+HD (v=1,j=2)→ SH+D/SD+H反应

Stereodynamic Control of Reactive Collisions of Cold Molecules: The S(1D)+ HD (v = 1, j = 2) → SH + D/SD + H Reaction

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  • 立体动力学旨在制备特定量子态与空间取向的分子,探究其对反应结果的影响,从而实现对化学反应的精确调控。目前,冷分子反应性碰撞的立体调控研究仍待探索。本文采用含时量子波包方法,在0.001-0.012 eV的低碰撞能范围内,研究了立体动力学调控对S(1D)+HD (v=1,j=2)→ SH+D/SD+H反应动力学结果及其量子效应的影响,研究发现,垂直碰撞构型因有利于插入机制而展现出最高的反应活性。在微分散射截面中,SD+H通道呈现符合长寿命中间体统计衰变的前后对称“U”型分布,而SH+D通道则表现出强前向散射。通过随机相位近似与干涉项分解分析证实,SH+D通道的前向散射是由不同反应分波在极小散射角区域发生的强前向相长干涉所主导。

     

    Stereodynamical control aims to prepare molecules in specific quantum states and spatial alignments to investigate their influence on reaction outcomes, thereby enabling precise regulation of chemical reactions. At present, stereodynamical control of reactive collisions of cold molecules remains to be explored. In this work, using a time-dependent quantum wave packet method, the stereodynamical control of the two product channels of the S(1D) + HD reaction for different initial alignment angles (β = 0°, 45°, 90°) of the HD (v = 1, j = 2) reactant within a low collision energy range of 0.001-0.012 eV is systematically investigated, based on a high-precision potential energy surface. The results reveal that the perpendicular collision configuration (β = 90°) exhibits the highest reactivity due to its favorable insertion mechanism. Moreover, the reaction always preferentially breaks the H-D bond to form the SH + D channel, with the branching ratio σSDSH remaining less than 1 under all conditions and increasing slowly with increasing collision energy. The differential cross section analysis reveals distinct angular distributions for the two channels: the SD + H channel displays a forward-backward symmetric “U-shaped” distribution, consistent with the statistical decay of a long-lived intermediate complex, whereas the SH + D channel exhibits a strong forward-scattering preference. Through random phase approximation and interference term decomposition analysis, it is confirmed that the forward scattering in the SH + D channel is dominated by strong constructive forward-angle interference among different partial waves in the region of very small scattering angles. Finally, the results of the Generalized Deflection Function further indicate that the product scattering is sensitive to changes in reactant alignment, which mainly originates from the variation of interference effects among different J partial waves with the alignment.This work provides a theoretical basis for understanding stereodynamical control and quantum interference in insertion-dominated reactions at low collision energies.

     

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