Quantitative and mechanistically detailed kinetics of the reaction of hydroxyl radical (OH) with carbon monoxide (CO) have been a longstanding goal of contemporary chemical kinetics. This fundamental prototype reaction plays an important role in atmospheric and combustion chemistry, motivating studies for accurate determination of the reaction rate coefficient and its pressure and temperature dependence at thermal reaction conditions. This intricate dependence can be traced directly to details of the underlying dynamics (formation, isomerization, and dissociation) involving the reactive intermediates cis- and trans-HOCO, which can only be observed transiently. Using time-resolved frequency comb spectroscopy, comprehensive mechanistic elucidation of the kinetics of the isotopic analog deuteroxyl radical (OD) with CO has been realized. By monitoring the concentrations of reactants, intermediates, and products in real time, the branching and isomerization kinetics and absolute yields of all species in the OD + CO reaction are quantified as a function of pressure and collision partner.

中文翻译：

---

直接测量OD + CO动力学中的DOCO异构体。

羟基自由基（OH）与一氧化碳（CO）反应的定量和机理详细动力学已成为现代化学动力学的长期目标。这个基本的原型反应在大气和燃烧化学中起着重要的作用，促使人们进行研究以准确确定反应速率系数及其在热反应条件下的压力和温度依赖性。这种复杂的依赖关系可以直接追溯到涉及反应中间体顺式和反式的基础动力学（形成，异构化和解离）的细节。-HOCO，只能瞬时观察到。使用时间分辨频率梳谱，已经实现了对具有CO的同位素类似物氘代氧自由基（OD）动力学的综合机理解释。通过实时监控反应物，中间体和产物的浓度，OD + CO反应中所有物种的支化和异构化动力学以及绝对收率可以根据压力和碰撞对象进行定量。