Ozone kinetics in low-pressure discharges: Vibrationally excited ozone and molecule formation on surfaces

A combined experimental and modeling investigation of the ozone kinetics in the afterglow of pulsed direct current discharges in oxygen is carried out. The discharge is generated in a cylindrical silica tube of radius 1 cm, with short pulse durations between 0.5 and 2 ms, pressures in the range 1-5 Torr and discharge currents ∼40-120 mA. Time-resolved absolute concentrations of ground-state atoms and ozone molecules were measured simultaneously in situ, by two-photon absorption laser-induced fluorescence and ultraviolet absorption, respectively. The experiments were complemented by a self-consistent model developed to interpret the results and, in particular, to evaluate the roles of vibrationally excited ozone and of ozone formation on surfaces. It is found that vibrationally excited ozone, , plays an important role in the ozone kinetics, leading to a decrease in the ozone concentration and an increase in its formation time. In turn, the kinetics of is strongly coupled with those of atomic oxygen and O₂(a ¹Δ_g) metastables. Ozone formation at the wall does not contribute significantly to the total ozone production under the present conditions. Upper limits for the effective heterogeneous recombination probability of O atoms into ozone are established.