The Extent of Non–Born-Oppenheimer Coupling in the Reaction of Cl(2P) with para-H2
The Extent of Non–Born-Oppenheimer Coupling in the Reaction of Cl(2P) with para-H2
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DOI：
10.1126/science.1163195
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发表时间：
2008-10
期刊：
影响因子：
56.9
通讯作者：
Xingan Wang;Wenrui Dong;C. Xiao;Li Che;Zefeng Ren;D. Dai;Xiuyan Wang;P. Casavecchia;Xueming Yang;B. Jiang;D. Xie;Zhigang Sun;Soo-Y. Lee;Dong H. Zhang;H. Werner;M. Alexander
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文献类型：
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作者：
Xingan Wang;Wenrui Dong;C. Xiao;Li Che;Zefeng Ren;D. Dai;Xiuyan Wang;P. Casavecchia;Xueming Yang;B. Jiang;D. Xie;Zhigang Sun;Soo-Y. Lee;Dong H. Zhang;H. Werner;M. Alexander
基本三原子反应提供了一个令人信服的测试，我们的理解的程度的电子-核耦合的化学反应，这是被忽视的广泛应用的玻恩-奥本海默（BO）近似。BO近似预测，在氯原子与氢分子的反应中，激发态的自旋轨道态（Cl*）不应参与到显着的程度。我们报告的分子束实验，氢原子里德伯标记检测的基础上，揭示只有一个次要的作用Cl*。这些结果与基于两组从头算势能面的完全量子反应散射计算非常一致。这项研究解决了以前的理论和实验之间的分歧，并确认我们有能力准确地模拟多个势能面上的化学反应。
Elementary triatomic reactions offer a compelling test of our understanding of the extent of electron-nuclear coupling in chemical reactions, which is neglected in the widely applied Born-Oppenheimer (BO) approximation. The BO approximation predicts that in reactions between chlorine (Cl) atoms and molecular hydrogen, the excited spin-orbit state (Cl*) should not participate to a notable extent. We report molecular beam experiments, based on hydrogen-atom Rydberg tagging detection, that reveal only a minor role of Cl*. These results are in excellent agreement with fully quantum-reactive scattering calculations based on two sets of ab initio potential energy surfaces. This study resolves a previous disagreement between theory and experiment and confirms our ability to simulate accurately chemical reactions on multiple potential energy surfaces.