Laser initiated half reaction study of H+O2→OH+O

Abstract

The HϩO 2 reaction system was studied under geometry limited half reaction conditions. The weakly bonded complex O 2 -H 2 S was formed by supersonic expansion, and reaction was initiated by 193 nm photoirradiation of the complex. Rotational, spin-orbit, and lambda doublet state distributions of product OH were determined by a laser-induced fluorescence ͑LIF͒ technique. The populations of the two spin-orbit states were observed to be statistical. The population of the ⌸͑AЈ͒ level was almost twice that of the ⌸͑AЉ͒ level, and the planar geometry was suggested for reaction path. These populations of the fine structures of OH were similar to those of OH formed under bimolecular reaction conditions. On the other hand, the rotational state distribution of OH from the half reaction has two components and the dominant one shows a very cold rotational distribution, in sharp contrast with that of the bimolecular reaction where rotation is highly excited. This cold rotational distribution could be partially explained by the absorption of a part of available energy by the internal motion of SH. However, the distribution with a peak at the lowest rotational level could not be explained by this effect, but ascribed to the exit interaction between SH and OH and/or the entrance channel specificity, i.e., the reaction occurs in limited impact parameters.

Quantum Dynamical Calculation of Bound Rovibrational States of HO2 up to Largest Possible Total Angular Momentum, J ≤ 130

“…The hydroperoxyl radical, HO 2 , has received very substantial experimental − and theoretical − interest over the last two decades. Far from abating over time, this interest seems only to have increased in recent years.…”