Improved Spectroscopic Data Synthesis for I2(B3ΠOu+) and Predictions of J Dependence for B(3ΠOu+)–X(1Σg+) Transition Intensities

Abstract

Some new techniques are introduced in a reanalysis of the spectroscopic data for I₂(B³Π_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(³Π_Ou⁺)–X(¹Σ_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.