The vibrational relaxation of O3 by He, D2 and H2

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Abstract
The rate constants for the vibrational relaxation of O3 by He, D2, n‐H2, and p‐H2 were measured over the temperature range 164 to 413 K. Visible chemiluminescence from the laser enhanced reaction NO+O3(001) was used to monitor the decay of vibrationally excited ozone. D2 was found to relax O3 more efficiently than He, with the ratio of relaxation probabilities PD2/PHe varying inversely with temperature. n‐H2 relaxed O3 more efficiently than p‐H2, with Pn‐H2/Pp‐H2 increasing with temperature. Also Pp‐H2/PD2 was found to be insensitive to temperature, having a value of 4±1. The data are compared with a semiclassical model which takes into account both VT and VR interactions. The variation of PD2/PHe appears to be due to D2 rotation. The behavior of Pn‐H2/Pp‐H2 can be explained by a near‐resonant VR transition occurring only with o‐H2. The Pp‐H2/PD2 ratio appears to be simply a mass effect, and can be accounted for with a VT model.

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