Transition Probabilities III. Dipole Velocity Computations for C2 and N2+. The Question of Degree of Hybridization

Abstract

Previous computations of transition probabilities for hydrogen using the dipole velocity operator are here extended to the diatomic molecules C₂ and N₂⁺ with particular reference to the former. Whereas previous calculations have shown the dipole length method to be relatively insensitive to the effective nuclear charge, the present computations show great sensitivity of the dipole velocity method to the ratio of the effective Z of the bonding orbital to that of the antibonding orbital. The results are less sensitive to the absolute magnitude of the Z's. The results are discussed with respect to reasonable assignments for the degree of s and pσ‐hybridization of the respective orbitals and with respect to reasonable choices for the effective Z values. It is concluded that the degree of hybridization is most probably considerably higher than previously estimated. The dipole velocity method is a promising one for further development.