A spectroscopic model for the low-lying electronic states of NO.

The rovibronic structure of AΣ, BΠ, and CΠ states of nitric oxide (NO) is studied with the aim of producing comprehensive line lists for its near ultraviolet spectrum. Empirical energy levels for the three electronic states are determined using a combination of the empirical measured active rotation-vibration energy level (MARVEL) procedure and ab initio calculations, and the available experimental data are critically evaluated. Ab initio methods that deal simultaneously with the Rydberg-like AΣ and CΠ and the valence BΠ state are tested. Methods of modeling the sharp avoided crossing between the BΠ and CΠ states are tested. A rovibronic Hamiltonian matrix is constructed using the variational nuclear motion program Duo whose eigenvalues are fitted to the MARVEL. The matrix also includes coupling terms obtained from the refinement of the ab initio potential energy and spin-orbit coupling curves. Calculated and observed energy levels agree well with each other, validating the applicability of our method and providing a useful model for this open shell system.