Evidence of Nonrigidity Effects in the Description of Low-Energy Anisotropic Molecular Collisions of Hydrogen Molecules with Excited Metastable Helium Atoms,Journal of Chemical Theory and Computation

当前位置： X-MOL 学术 › J. Chem. Theory Comput. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Evidence of Nonrigidity Effects in the Description of Low-Energy Anisotropic Molecular Collisions of Hydrogen Molecules with Excited Metastable Helium Atoms
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2020-03-09 , DOI: 10.1021/acs.jctc.0c00183
Mariusz Pawlak ₁ , Piotr S. Żuchowski ₂ , Nimrod Moiseyev ₃ , Piotr Jankowski ₁

Affiliation

Cold collisions serve as a sensitive probe of the interaction potential. In the recent study of Klein et al. (Nature Phys.2017, 13, 35–38), the one-parameter scaling of the interaction potential was necessary to obtain agreement between theoretical and observed patterns of the orbiting resonances for excited metastable helium atoms colliding with hydrogen molecules. Here, we show that the effect of nonrigidity of the H₂ molecule on the resonant structure, absent in the previous study, is critical to predict the correct positions of the resonances in that case. We have complemented the theoretical description of the interaction potential and revised reaction rate coefficients by proper inclusion of the flexibility of the molecule. The calculated reaction rate coefficients are in remarkable agreement with the experimental data without empirical adjustment of the interaction potential. We have shown that even state-of-the-art calculations of the interaction energy cannot ensure agreement with the experiment if such an important physical effect as flexibility of the interacting molecule is neglected. Our findings about the significance of the nonrigidity effects can be especially crucial in cold chemistry, where the quantum nature of molecules is pronounced.

中文翻译：

低刚性各向异性分子碰撞氢原子的低能各向异性分子碰撞中非刚性效应的证据

冷碰撞是相互作用潜力的敏感探针。在Klein等人的最新研究中。（自然的PHY。2017，13，35-38），交互电位的单参数缩放是必要的，以获得激亚稳态氦原子与氢分子碰撞回旋共振的理论和观察到的模式之间的一致性。在这里，我们证明了H ₂的非刚性影响以前的研究中缺少共振结构上的分子，对于预测这种情况下共振的正确位置至关重要。通过适当包含分子的柔韧性，我们对相互作用势和修正的反应速率系数的理论描述进行了补充。计算出的反应速率系数与实验数据非常吻合，而无需对相互作用电位进行经验调整。我们已经表明，如果忽略了重要的物理效应（如相互作用分子的柔韧性），即使是最新的相互作用能计算也无法确保与实验相符。我们关于非刚性效应重要性的发现在冷化学中尤为重要，因为在冷化学中，分子的量子性质很明显。

更新日期：2020-04-24

点击分享查看原文

点击收藏

公开下载

阅读更多本刊最新论文本刊介绍/投稿指南11