Fine‐Structure analysis of ClO fragments in the mode‐specific predissociation of chlorine dioxide

Abstract

AbstractThe photodissociation of OClO (2A2) ClO (X2πΩ,ν,J,Λ)+O (3P) in the 424‐450 nm region and in the 356‐371 nm region has been investigated by monitoring the ClO (X2πΩ,ν = 0,J,ν) fragments using two‐photon laser‐induced fluorescence. In the long‐wavelength regime the product vibrational excitation is clearly a function of the particular initial type of motion of OClO (2A2v1,v2,V3). This behavior is significantly reduced at shorter photolysis wavelengths. The population of the fragments rotational levels is observed to resemble Boltzmann distributions of around 1000 K. A population ratio of about P(2π3/2): P(2π1/2) = 3.5 is obtained for the two spin‐orbit states of ClO. The ν‐doublet states (A′) and (A″) of the ClO fragments are equally preferred in the dissociation process.