Chemistry, Ames Laboratory
Journal or Book Title
Journal of Chemical Physics
Accurate spin–orbit splitting constants (Av+) for the vibrational levels v+=0–41 of CO+(A 2Π3/2,1/2) have been determined in a rotationally resolved pulsed field ionization photoelectron study. A change in slope is observed in the v+ dependence for Av+ at v+≈19–20. This observation is attributed to perturbation of the CO+(A 2Π) potential by the CO+(B 2Σ+) state. Theoretical Av+ values for CO+(A 2Π3/2,1/2, v+=0–41) have also been obtained using a newly developed ab initio computational routine for spin–orbit coupling calculations. The theoretical Av+ predictions computed using this routine are found to be in agreement with the experimental Av+ values for CO+(A 2Π3/2,1/2, v+=0–41). Similar Av+calculations obtained for O+2(X 2Π3/2,1/2g, v+=0–38) are also in accord with the recent experimental Av+ values reported by Song et al. [J. Chem. Phys. 111, 1905 (1999)].
Copyright 1999 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.
American Institute of Physics
Fedorov, Dmitri G.; Evans, M.; Song, Y.; Gordon, Mark S.; and Ng, C. Y., "An Experimental and Theoretical Study of the Spin–Orbit Interaction for CO+(A 2Π3/2,1/2, v+=0–41) and O+2(X 2Π3/2,1/2g, v+=0–38)" (1999). Ames Laboratory Publications. 322.