Mode-selective chemistry and quantum state resolved polyatomic reaction dynamics

该项目研究多原子反应的量子态特定动力学，并打算开发概念来理解这些系统中发生的模式选择化学。虽然对三原子反应和选定的四原子反应已经达到了完全量子态解析的理解水平，但将这种理解水平扩展到涉及更多原子的反应是一个具有挑战性的课题。甲烷与原子或双原子分子（如氢、氯、氧或氢氧根）的反应是大气化学和燃烧化学中的重要过程。它们也是基础研究广泛研究的典型多原子反应，重点是对化学反应性的详细了解。实验研究取得了令人印象深刻的进展，证明了这些系统中发生的模式选择化学。然而，理论研究大多基于降维模型或准经典轨迹模拟。本项目采用精确的全维量子动力学方法来研究甲烷与H、Cl和OH的反应。具体地说，波包动力学计算利用多层多构型时变哈特里方法和通量相关函数来促进这些六原子和七原子反应的详细研究。结果将与实验观察结果进行比较。中心目标是发展一般概念，以理解多原子反应中的模式选择化学。

The project studies the quantum state-specific dynamics of polyatomic reactions and intends to develop concepts to understand the mode-selective chemistry occurring in these systems. While a fully quantum state resolved level of understanding has been achieved for triatomic and selected tetratomic reactions, extending this level of understanding towards reactions involving a larger number of atoms is a challenging subject. Reactions of methane with atoms or diatomic molecules, e.g., H, Cl, O, or OH, are important processes in atmospheric and combustion chemistry. They are also prototypical polyatomic reactions extensively studied by fundamental research focusing on the detailed understanding of chemical reactivity. Impressive progress was achieved in experimental studies which demonstrated the mode-selective chemistry occurring in these systems. However, theoretical investigation are mostly based on reduced-dimensional models or quasi-classical trajectory simulations. In this project accurate full-dimensional quantum dynamics methods are used to study the reactions of methane with H, Cl, and OH. Specifically, wave packet dynamics calculations utilizing the multi-layer multi-configurational time-dependent Hartree approach and flux correlation functions will be employed to facilitate the detailed investigation of these six and seven atom reactions. The results will be compared to experimental observations. The central aim is the development of general concepts for the understanding of the mode-selective chemistry in polyatomic reactions.