ELEMENTARY PROCESSES IN THE DECOMPOSITION OF OZONE

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Abstract
Potential-energy surfaces are considered for the O4 complex, treated as the three-body complex O … O … O2. By means of these it is shown that O(3P) reacting with O3 may give rise to a molecule of O2 in its ground state and one in any of the states 3Σg− (ground), 1Δg, and 1Σg+; 3Σu+ cannot be produced. Most of the oxygen molecules produced are expected to be in the ground electronic state, but will be vibrationally excited. Such molecules are readily deactivated and unlikely to lead to energy chains by the reaction[Formula: see text]Such chains are therefore unlikely in the thermal decomposition and in that initiated by visible radiation. In ultraviolet light O(1D) atoms are produced and the potential-energy surfaces show that these give rise very efficiently to O(1D) + O3 → O2 + O2(3Σu−); the latter have 141 kcal in excess of the ground state. It is suggested that the subsequent radiative process[Formula: see text]is responsible for sustaining the population of vibrationally excited oxygen molecules in the ground state and that these propagate energy chains, as postulated by McGrath and Norrish (1). The significance of these conclusions is discussed with reference to the experimental evidence.

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