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

The thermal and photochemical reactivity of the symmetric isomer of ch lorine dioxide, OClO, is examined under isolated molecule conditions a nd 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 ga s phase. Chemistry on the excited electronic manifold occurs via multi ple 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 OC lO in water solution is significantly different from the gas phase pro cess. The effect of solvent on the excited state photoreactivity of OC lO is discussed in detail.