Vibrationally and Rotationally State-Resolved Differential Cross Sections for Reactive Scattering

俄克拉荷马大学的Mark Keil和Gregory A. Parker在实验物理化学项目的支持下，继续对各种简单反应的状态-状态反应动力学进行研究：(i)氟原子与氢二聚体形成氟化氢；（二）氟原子和氯化氢形成氟化氢和氯原子；（三）氯原子和溴化氢形成氯化氢和溴原子。我们感兴趣的反应发生在两个交叉分子束的交叉处。然后使用高分辨率化学激光器与测热计探测器结合来解析散射产物的振动旋转状态和角分布。pi将探索不同初始旋转和动能以及同位素取代对振动和旋转状态分辨微分截面的影响。直接比较将与从头算理论动力学计算使用量子散射码开发的co-PI。这些研究的主要目的是加深我们对化学反应动力学在详细的状态到状态水平的理解。利用近似技术简化日益复杂的化学反应性问题，目前正在取得巨大的理论进展。在这种量子计算中使用的近似的有效性通常是基于对这里研究的那种三原子A+BC系统的经验：对A+BC系统的详细研究为理解更大的系统提供了基础。详细的化学反应动力学领域有助于广泛地阐明化学反应性，与化学的所有分支都有明显的相关性。

Mark Keil and Gregory A. Parker of the University of Oklahoma are supported by the Experimental Physical Chemistry Program to continue their investigations on state-to-state reaction dynamics for various simple reactions: (i) fluorine atoms plus hydrogen dimer to form hydrogen fluoride; (ii) fluorine atoms and hydrogen chloride to form hydrogen fluoride and chlorine atoms; (iii) chlorine atoms and hydrogen bromide to form hydrogen chloride and bromine atoms. The reaction of interest takes place at the intersection of two crossed molecular beams. A high-resolution chemical laser in conjunction with a bolometer detector is then used to resolve the scattered product vib-rotational state and angular distribution. The PIs will explore the effects of varying initial rotational and kinetic energies, and isotopic substitutions, upon the vibrationally and rotationally state-resolved differential cross sections. Direct comparisons will be made with ab initio theoretical dynamical calculations using quantum scattering codes developed by the co-PI. The principal goal of these studies is to deepen our understanding of chemical reaction dynamics at the detailed state-to-state level. Tremendous theoretical progress is currently being made using approximation techniques for simplifying increasingly complex chemical reactivity problems. The validity of approximations used in such quantum calculations is often based upon experience with tri-atomic A+BC systems of the sort studied here: detailed investigations of A+BC systems have provided the foundation upon which larger systems can be understood. The field of detailed chemical reaction dynamics is helping elucidate chemical reactivity very broadly, with obvious relevance to all branches of chemistry.