Dependence of the chemiluminescence cross section on spinhyphen;orbit state for the reaction of Ca(3P0J) with alkyl bromides

摘要

The dependence of the chemiluminescence cross section on initial spinhyphen;orbit level has been measured for the reaction of metastable Ca(4s4p3P0J) with Cl2, CH3Br, CH2Br2, CH2=CHCH2Br, and C6H5CH2Br, using an optical pumping state selection technique. Optical pumping depletion was also used to determine what fraction of the chemiluminescence was due to the second metastable Ca(4s3dthinsp;1D) level present in the incident atomic beam. Chemiluminescence cross sections for both the3P0and1Dreactions were separately determined; total attenuation and intramultiplet mixing cross sections were also estimated. The Ca(3P0) spinhyphen;orbit dependence for the chemiluminescence channel in all the reactions studied was substantial and of similar magnitude, with an order of reactivityJ=2J=1J=0. This spinhyphen;orbit selectivity is related to differences in the evolution of the asymptotic spinhyphen;orbit states onto the various electrostatic surfaces at smaller separations. It is remarkable that this selectivity persists with polyatomic reagents.