Ping Leilei, Tian Li, Song Hongwei, Yang Minghui
State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics , Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences , Wuhan 430071 , China.
College of Physical Science and Technology , Huazhong Normal University , Wuhan 430079 , China.
J Phys Chem A. 2018 Sep 6;122(35):6997-7005. doi: 10.1021/acs.jpca.8b06662. Epub 2018 Aug 28.
State-to-state reaction dynamics provides a comprehensive insight into reaction mechanisms of chemical reactions at the atomic level. A new scheme to extract final-state information based on normal mode analysis is proposed in this work. Different from the traditional scheme extracting the coordinates and momenta from the last step of each trajectory, they are taken in the new scheme from a specific step of each reactive trajectory within the last vibrational period of the product molecule by demanding the corresponding geometry of the step to have the minimum potential energy. Test calculations on the collisions between the atom H and the molecules HO, HS, and NH show that the new scheme works much better than the traditional one. In addition, the new scheme is applied to calculate the vibrational state distribution of the product NH in the reaction H + NH → H + NH.
态-态反应动力学在原子水平上全面深入地揭示了化学反应的机理。本文提出了一种基于简正模式分析提取末态信息的新方案。与传统方案从每条轨迹的最后一步提取坐标和动量不同，新方案是在产物分子最后一个振动周期内，通过要求特定步骤的相应几何结构具有最小势能，从每条反应轨迹的特定步骤中获取坐标和动量。对氢原子与HO、HS和NH分子间碰撞的测试计算表明，新方案比传统方案效果好得多。此外，新方案还被用于计算反应H + NH → H + NH中产物NH的振动态分布。
