Transition Probabilities. II. Calculation of Semi-Theoretical f-Numbers for Hydrogen Using the Dipole Velocity Operator

Abstract

The computations of Mulliken and Rieke using the LCAO MO and the AO methods for transition probabilities of the Lyman (¹Σ_g⁺—¹Σ_u⁺) and Werner (¹Σ_g⁺—¹π_u) transitions in hydrogen have been repeated using the alternative velocity form of the transition moment operator. It is found that, for an effective Z value of 1.2 for the 1s AO (the variation value) and a suitable Rydberg form for the excited state, the transition probabilities calculated from these two operators agree well. In addition there is quite good agreement between the AO and MO methods in each instance and between the calculated and experimental value for the sum of the strengths of the Lyman and Werner transitions.