Rotational analysis of the 7390- and 7937-Å bands of NO2 by means of Fourier transform spectroscopy

We have extended to higher N and to K_a = 3 and 4 the rotational analysis of the 7390-Å band of NO₂ performed by K. E. Hallin and A. J. Merer (Canad. J. Phys.55, 2101–2112 (1977)). The lines belong to a perturbed parallel band for which Hallin and others have proposed the vibrational assignment (2 13 1)-(0 0 0) within the electronic ground state. These authors presumed that this band borrows its intensity through a vibronic coupling (spin-orbit and/or Coriolis coupling) from the stronger (0 2 0)-(0 0 0) band of the $\text{A}\text{?}\text{-}\text{X}\text{?}$ electronic system at 7460 Å. We have observed about 900 transitions belonging to the K_a = 0, 1, 2, 3, 4 subbands of the (2 13 1)-(0 0 0) band for N values going up to about 23, and 300 lines of the “hot” band (2 13 1)-(0 1 0). We have also looked for spin-orbit-induced transitions and we have detected about 400 transitions with ΔN ≠ ΔJ. Among them ΔN = ±2 transitions with ΔK_a = 0 or ± 2 have been observed, indicating that N and K_a are no longer good quantum numbers, and demonstrating clearly the existence of rovibronic interactions perturbing the upper levels of the transitions.