An experimental and theoretical study of the spin-orbit interaction for CO~+(A~2#PI#_(3/2,1/2), V~+ = 0-41) and O_2~+(X~2#PI#_(3/2,1/2g), V~+ = 0-38)

摘要

Accurate spin-orbit splitting constants (A_(v+)) for the vibrational levels v~+ = 0-41 of CO~+(A ~2#PI#_(3/2,1/2)) have been determined in a rotationally resolved pulsed field ionization photoelectron study. A change in slope is observed in the v~+ dependence for A_(v+) at v~+ approx=19-20. This observation is attributed to perturbation of the CO~+(A ~2#PI#) potential by the CO~+ (B ~2#SIGMA#~+) state. Theoretical A_(v+) values for CO~+(A ~2#PI#_(3/2,1/2), v~+ = 0-41) have also been obtained using a newly developed ab initio computational routine for spin-orbit coupling calculations. The theoretical A_(v+) predictions computed using this routine are found to be in agreement with the experimental A_(v+) values for CO~+(A ~2#PI#_(3/2,1/2), v~+ = 0-41). Similar A_(v+) calculations obtained for O_2~+(X ~2#PI#_(3/2,1/2g), v~+ = 0-38) are also in accord with the recent experimental A_(v+) values reported by Song et al. [J. Chem. Phys. 111, 1905 (1999)].