DYNAMICS STUDIES OF THE CHEMILUMINESCENT REACTIONS OF ClO2 WITH Ca (S-1, P-3) AND Ba (S-1, D-3)

The chemiluminescent reactions of clo2 with ca, ba atoms have been studied under single collision conditon in a beam-gas apparatus. the metastable states of the metal atoms are generated by the use of low voltage dc discharge. the chemiluminescence spectra have been observed ad the spatial distributions of the intensities of the chemiluminescent emissions have been also measured by oma-ii. the total reaction cross sections of metal atoms measured are 97 angstrom(2), 138 angstrom(2) for ca(s-1), ca(p-3)a nd 138 angstrom(2), 230 angstrom(2) for ba(s-1), ba(d-3) respectively. the intensities of the chemiluminescence spectra are increased significantly when the metal atoms are excited to their metastable states. in particular, the increase of bao(a') is much more than that of bacl (c) in the reactio of ba(d-3) + clo2. in addition, non-boltzmann vibrational distributions were found in the electronic excited state a' (1)pi of the products mo in both reacations by computer simulation. the chemiluminescent cross sections of the transition c-2 pi -> x-2 sigma(+) of the products mcl are 51 angstrom(2) for ba(d-3) +clo2, 31 angstrom(2) for ca(p-3) + clo2 respectively. the branching ratios of the products mo and mcl were calculated based ont he chemiluminescent spectra. a discussin about the mechanisms of these reactions is presented.