The electronic structure of the first row hydrides BH, CH, NH, OH and FH II. Excited states

Abstract

Previous calculations on the ground states of the hydrides are extended to include the stable excited states. The ab initio orbital calculations predict vertical excitation energies which differ from the experimental values by as much as 2eV. However, when allowance is made for the effects of atomic electron correlation all errors in the calculated excitation energies become less than 0·2eV. The locations of excited states of different multiplicities from those of the ground states are predicted to within this accuracy. The oscillator strengths of allowed transitions from the ground states are calculated using both the dipole-length and dipole-velocity formulae. The dipole-length values are in fair agreement with the only experimental value available (for OH 2 ll → 2 ∑ + ), whereas the dipole-velocity values are much too large. Possible improvements in the accuracy of the calculations are discussed.