Abstract
The O 2 + b 4 Σ g −-a 4 Π u First Negative band system has been extended to the v = 3 level of the upper state by photographing the (3, 1) band in high resolution. This and other newly recorded bands and the previously measured bands of this system have been reduced to molecular constants using a method to merge the least-squares results of separate band-by-band fits. First, the line positions of each are fitted separately, and second, these band-by-band results have been combined to obtain the best single values of each molecular constant of each vibrational level v′ ≤ 3 and v″ ≤ 6. It is found that anomalies in the fine-structure splittings of the a 4Π u state can be accounted for fully by including the diagonal and off-diagonal elements of the phenomenological spin-spin Hamiltonian. The information contained in blended lines is partially recovered by using calculated line intensities to resolve ambiguities in their assignments. Particular attention has been paid to the strong correlation between the centrifugal distortion spin-orbit constant A D and the spin-rotation constant γ of the a 4Π u state. Dunham Y ij coefficients are obtained for both states. A previously unnoticed possible perturbation in the v = 3 level of the a 4Π u state has been found.
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