PNO-CEPA and MCSCF-SCEP calculations of transition probabilities in OH, HF+, and HCl+

Abstract

Electronic transition moment functions for the A 2Σ +-X 2Π transitions in OH, HF+, and HCl + have been calculated using RHF, PNO-CI, PNO-CEPA, MCSCF, and MCSCF-SCEP wave functions. The vibrational band transition probabilities are obtained, and the resulting radiative lifetimes are compared with measured values. For OH and HCl+ the deviations are smaller than 10%, but the theoretical lifetimes for HF+ are larger by about 300% than the experimental values. For the electronic ground states of HF+ and HCl+ vibrational transition probabilities have been calculated from MCSCF-SCEP dipole moment functions. Both ions are predicted to be excellent absorbers and emitters in the infrared spectral region. © 1984 American Institute of Physics.