RECENT PROGRESS IN INFRARED ABSORPTION TECHNIQUES FOR ELEMENTARY GAS-PHASE REACTION KINETICS

Sensitive and precise measurements of rate coefficients, branching fractions, and energy disposal from gas-phase radical reactions provide information about the mechanism of elementary reactions as well as furnish modelers of complicated chemical systems with rate data. This chapter describes the use of time-resolved infrared laser absorption as a tool for investigating gas-phase radical reactions, emphasizing the exploitation of the particular advantages of the technique. The reaction of Cl atoms with HD illustrates the complementarity of thermal kinetic measurements with molecular beam data. Measurements of second-order reactions, such as the self-reactions of SiH3 and C3H3 radicals, and determinations of product branching fractions in reactions such as CN + O2 rely on the wide applicability of infrared absorption and on the straightforward relationship of absorption to absolute concentration. Finally, investigations of product vibrational distributions, as in the CN + H2 reaction, provide additional insight into the details of reaction mechanisms.