On the energy dependence of the hyperfine interaction in excited states of NO2

Abstract

We report on the hyperfine structure of N=1, J=3/2 levels of 62 NO2 vibronic states in the 16 850–21 500 cm−1 region, as determined via quantum beat spectroscopy. The hyperfine structure of these levels of mixed à 2B2/X̃ 2A1 electronic character is dominated by the X̃ 2A1 Fermi-contact interaction, and a decrease in the hyperfine splittings with increasing energy is revealed when our results are compared with previous studies in the 11 200–13 700 cm−1 region. This comparison also reveals the loss of a correlation between band intensity and Fermi-contact constant. A detailed comparison of our results with theoretical predictions for the 16 600–18 700 cm−1 region is presented. We find that vibrational averaging of the X̃ 2A1 Fermi-contact interaction is reflected in the hyperfine interaction of bands in this region, and should also be a factor in producing the small hyperfine splittings observed at energies near dissociation threshold.