Laser induced dispersed fluorescence spectra of jet cooled NO2: The complete set of vibrational levels up to 10 000 cm−1 and the onset of the X̃ 2A1–Ã 2B2 vibronic interaction

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Abstract
The laser induced dispersed fluorescence spectra (L.I.D.F.S.) of jet cooled NO2 molecules in emission from 11 different vibronic levels located between 22 006 and 23 625 cm−1 was recorded. The corresponding variety of Franck–Condon accesses has allowed the observation of the complete set of the 191 lowest vibrational levels of the X̃ 2A1 ground state, located up to 10 000 cm−1. The vibrational band origins were measured to within typically 0.3 cm−1, assigned (n1, n2, n3), and fitted with a 24 coefficient Dunham expansion giving a typical residual error of 0.5 cm−1. Furthermore, the vibrationless à 2B2 level has probably also been observed at 9737 cm−1. A perturbative model of the X̃ 2A1–à 2B2 vibronic interaction has been used in order to calculate the energy shift of the high vibrational levels (around 10 000 cm−1) of the X̃ 2A1 state.

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