TY - JOUR
AU - Thinh Bui
AU - Bryce Bjork
AU - Bryan Changala
AU - Thanh Nguyen
AU - John Stanton
AU - Mitchio Okumura
AU - Jun Ye
AB - 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\&nbsp;<em>cis</em>- and\&nbsp;<em>trans</em>-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.
BT - Science Advances
DA - 2018-01
DO - 10.1126/sciadv.aao4777
IS - 1
N2 - 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\&nbsp;<em>cis</em>- and\&nbsp;<em>trans</em>-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.
PY - 2018
EP - eaao4777
T2 - Science Advances
TI - Direct measurements of DOCO isomers in the kinetics of OD + CO
UR - http://advances.sciencemag.org/content/4/1/eaao4777
VL - 4
ER -