Time-resolved Frequency Comb Spectroscopy Research Articles

Direct measurements of DOCO isomers in the kinetics of OD + CO.

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.

OD + CO → D + CO2 branching kinetics probed with time-resolved frequency comb spectroscopy

Time-resolved direct frequency comb spectroscopy was used to study the kinetics of the OD+CO→D+CO2 reaction, which is important for atmospheric and combustion chemistry. Complementing our recent work on quantifying the formation rate of the trans-DOCO radical, we report measurements of the kinetics of the chemically activated product channel, D+CO2, at room temperature. Simultaneous measurements of the time-dependence of OD and CO2 concentrations directly yield the products’ formation rate and its dependence on pressure and bath gas. Together with the trans-DOCO formation rate, these new measurements provide absolute yields of branching channels for both products of OD+CO in the low-pressure limit.

Mid-Infrared Time-Resolved Frequency Comb Spectroscopy of Transient Free Radicals.

We demonstrate time-resolved frequency comb spectroscopy (TRFCS), a new broadband absorption spectroscopy technique for the study of trace free radicals on the microsecond timescale. We apply TRFCS to study the time-resolved, mid-infrared absorption of the deuterated hydroxyformyl radical trans-DOCO, an important short-lived intermediate along the OD + CO reaction path. Directly after photolysis of the chemical precursor acrylic acid-d1, we measure absolute trans-DOCO product concentrations with a sensitivity of 5 × 10(10) cm(-3) and observe its subsequent loss with a time resolution of 25 μs. The multiplexed nature of TRFCS allows us to detect simultaneously the time-dependent concentration of several other photoproducts and thus unravel primary and secondary chemical reaction pathways.