Mauguière Frédéric A L, Collins Peter, Stamatiadis Stamatis, Li Anyang, Ezra Gregory S, Farantos Stavros C, Kramer Zeb C, Carpenter Barry K, Wiggins Stephen, Guo Hua
School of Mathematics, University of Bristol , Bristol BS8 1TW, United Kingdom.
Department of Materials Science and Technology, University of Crete , Iraklion 710 03, Greece.
J Phys Chem A. 2016 Jul 14;120(27):5145-54. doi: 10.1021/acs.jpca.6b00682. Epub 2016 Mar 11.
The roaming mechanism in the reaction H + MgH →Mg + HH is investigated by classical and quantum dynamics employing an accurate ab initio three-dimensional ground electronic state potential energy surface. The reaction dynamics are explored by running trajectories initialized on a four-dimensional dividing surface anchored on three-dimensional normally hyperbolic invariant manifold associated with a family of unstable orbiting periodic orbits in the entrance channel of the reaction (H + MgH). By locating periodic orbits localized in the HMgH well or involving H orbiting around the MgH diatom, and following their continuation with the total energy, regions in phase space where reactive or nonreactive trajectories may be trapped are found. In this way roaming reaction pathways are deduced in phase space. Patterns similar to periodic orbits projected into configuration space are found for the quantum bound and resonance eigenstates. Roaming is attributed to the capture of the trajectories in the neighborhood of certain periodic orbits. The complex forming trajectories in the HMgH well can either return to the radical channel or "roam" to the MgHH minimum from where the molecule may react.
利用精确的从头算三维基态电子态势能面，通过经典动力学和量子动力学研究了反应H + MgH →Mg + HH中的漫游机制。通过在与反应（H + MgH）入口通道中一族不稳定轨道周期性轨道相关的三维正常双曲不变流形上的四维分界面上初始化轨迹，探索反应动力学。通过定位位于HMgH阱中或涉及H围绕MgH双原子轨道运动的周期性轨道，并随着总能量追踪它们的延续，发现了相空间中反应性或非反应性轨迹可能被困的区域。通过这种方式，在相空间中推导出漫游反应路径。对于量子束缚态和共振本征态，发现了与投影到构型空间中的周期性轨道相似的模式。漫游归因于轨迹在某些周期性轨道附近的捕获。在HMgH阱中形成复合物的轨迹既可以返回自由基通道，也可以“漫游”到MgHH最小值处，分子可能从该处发生反应。
