Improved Spectroscopic Data Synthesis for I₂(<i>B</i>³Π_Ou⁺) and Predictions of <i>J</i> Dependence for <i>B</i>(³Π_Ou⁺)–<i>X</i>(¹Σ_g⁺) Transition Intensities

Abstract

Some new techniques are introduced in a reanalysis of the spectroscopic data for I 2 (B 3 Π Ou + )to obtain a more complete and internally consistent set of molecular constants, and an RKR potential curve. In particular, attention is focussed on the determination of reliable high-order rotational constants (D ν , H ν , etc.) for highly excited vibrational levels. The ensuing intermolecular potential for this state is then used together with a known ground-state curve in a study of the J dependence of Franck-Condon factors for discrete B( 3 Π Ou + )–X( 1 Σ g + ) transitions over a wide range of ν and J. It is concluded that at the temperatures 1000–2000 °K routinely achieved in shock-tube experiments, the intensity of most vibrational bands will vary drastically as J ranges across the half-width of the thermal rotational population distribution.