Rotational line strengths in 3Δ–3Σ electronic transitions. The Herzberg III system of molecular oxygen

Abstract

Electronic transitions of the type 3Δ–3Σ are forbidden in the absence of spin–orbit or orbit–rotation coupling, but spin–orbit perturbations produce three transition moments, two perpendicular (Y1 and Y2) and one parallel (Z1) while low-order orbit–rotation couplings introduce three further perpendicular transition moments (X1, X2, and X3). Formulas are presented for the rotational line strengths in a 3Δ(a)–3Σ(int) transition in terms of these parameters and are applied to recent data of Coquart and Ramsay for the Herzberg III system [Formula: see text] of molecular oxygen. It is shown that all six parameters are significant, and that there are noticeable departures from the first-order relations Y1 = Y2, Z1 = 0, X1 = X2 = X3. The observation of orbit–rotation intensity effects led to the first identification of lines of the Ω′ = 3 subbands of the 4–0 to 7–0 bands of the Herzberg III system, which are forbidden for the spin–orbit mechanism. The wave numbers of these lines are in satisfactory agreement with the analysis of the A′3Δu → a1Δg emission by Slanger and Huestis.