The product vibrational, rotational, and translational energy distribution for the reaction O(3P J)+O3→2O2: Breakdown of the spectator bond mechanism

Abstract

Laser induced fluorescence (LIF) detection of highly vibrationally excited O2 resulting from visible photolysis of pure O3 is attributed to the title reaction. The vibrational and rotational energy distributions as well as Doppler profiles of selected product states of the nascent O2 were obtained. Predictions of quasiclassical trajectory calculations on the ‘‘Varandas-Pais’’ potential energy surface (l) are inconsistent with observation. This points out the need for a more accurate ab initio study of this important reaction. The implications for nonlocal thermodynamic equilibrium chemistry in the stratosphere are discussed.