The Reaction of Spin–Orbit State-Selected Ca(PJ03) With CH₃I, CH₂I₂, and SF₆

Abstract

Chemiluminescence cross sections for reaction of the individual spin–orbit states of metastable Ca(PJ03) with CH₃I, CH₂I₂, and SF₆ have been determined by the use of optical pumping state selection. This technique was also used to separate the chemiluminescence arising from the two excited metastable Ca ³P⁰ and ¹D states. The spin–orbit dependence of the chemiluminescence pathway was found to be substantial for the CH₃I and CH₂I₂ reactions and similar to that previously observed for halogen diatom and alkyl bromide reagents. By contrast, no spin–orbit effect was observed for Ca(³P⁰)+SF₆. These results are discussed in terms of our previously presented model for the origin of spin–orbit effects in chemical reactions.