COMPARISONS BETWEEN THE REACTIVITY OF CHLORINE DIOXIDE IN THE GAS-PHASE AND WATER SOLUTION

The thermal and photochemical reactivity of the symmetric isomer of chlorine dioxide, OClO, is examined under isolated molecule conditions and in water solution. Reaction in the ground state leads to Cl(P-2(u)) + 02(3SIGMA(g-)). Within experimental error, the barrier to reaction in water solution is the same as that estimated for the reaction in gas phase. Chemistry on the excited electronic manifold occurs via multiple pathways leading to ClO(2PI) + O(P-3(g)), Cl(P-2(u)) + 02(3SIGMA(g-)) and Cl(P-2(u)) + 02(1DELTA(g)). The excited state reactivity of OClO in water solution is significantly different from the gas phase process. The effect of solvent on the excited state photoreactivity of OClO is discussed in detail.