Millimeter-wave optical double resonance spectra of NO2: How good a quantum number is N?

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Abstract
Optical transitions to the 2B2 electronic state region of NO2 have been observed in double resonance with three millimeter-wave ground state rotational transitions. The probed ground state transitions were the N=2 (F1), N=4 (F1), and N=10 (F2), K=0→1 Q branch transitions near 250 GHz. The optical range scanned was 16 800 to 16 950 cm−1. The 100,10–101,9 F2 spectrum was combined with previous double resonance results with the ground state 91,9–100,10 F1 transition. This comparison shows 70 out of 160 upper states with J=19/2 to have indefinite or mixed N values. It establishes violations of the ΔN=ΔJ selection rule in this spectral region which contains bands with a wide range of spin-rotation constants. Lack of intensity correlation between the two spectra suggests two classes of upper states are present: a group of strongly N-mixed upper states, and a group essentially unmixed in N. Heller’s F parameter, which measures the fraction of all possible symmetry-restricted basis states contributing to a typical eigenstate, is similar for the double-resonance spectra of the three N values, but is greater for K=1 than for K=0. By finding upper states in common, R lines from N=2 and P lines from N=4 have been identified.