Dynamics of vibrationally excited ozone formed by three-body recombination. II. Kinetics and mechanism

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Abstract
Spectrally resolved infrared chemiluminescence from vibrationally excited ozone, O3(v), has been used to study the reaction kinetics of O3(v) in discharged O2/Ar mixtures at ∼1 Torr and 80–150 K. Dependences of the excited state number densities on temperature and O2 mole fraction indicate O3(v) is formed primarily by three‐body recombination of O with O2 and is destroyed by rapid chemical reaction with O. Several secondary excitation reactions involving vibrationally and electronically excited O2 are also indicated. The data are treated with a detailed steady‐state analysis of the discharge kinetics, to extract estimates for rate coefficients of the key elementary reactions. The effective ‘‘quasinascent’’ state distribution in recombination is also inferred; this distribution shows selective recombination into the asymmetric stretching mode, but an apparently statistical (i.e., collisionally scrambled) behavior among the vibrational states within that mode. The results are discussed in terms of the detailed dynamics of three‐body recombination.