The Reaction of Spin–Orbit State‐Selected Ca( PJ0 3) With CH3I, CH2I2, and SF6

Chemiluminescence cross sections for reaction of the individual spin–orbit states ofmetastable Ca(P J 03 ) with CH 3 I, CH 2 I 2 , and SF 6 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 3 P 0 and 1 D states. The spin–orbit dependence of the chemiluminescence pathway was found to be substantial for the CH 3 I and CH 2 I 2 reactions and similar to that previously observed for halogen diatom and alkyl bromide reagents. By contrast, no spin–orbit effect was observed for Ca( 3 P 0 )+SF 6 . These results are discussed in terms of our previously presented model for the origin of spin–orbit effects in chemical reactions.