A systematic theoretical investigation of the valence excited states of the diatomic molecules B₂, C₂, N₂ and O₂

A quantitative survey on the performance of multireference (MR), configuration interaction with all singles and doubles (CISD), MRCISD with the Davidson correction and MR-average quadratic coupled cluster (AQCC) methods for a wide range of excited states of the diatomic molecules B₂, C₂, N₂ and O₂ is presented. The spectroscopic constants r_e, ω_e, T_e and D_e for a total of 60 states have been evaluated and critically compared with available experimental data. Basis set extrapolations and size-extensivity corrections are essential for highly accurate results: MR-AQCC mean-errors of 0.001 A, 10 cm^-1, 300 cm^-1 and 300 cm^-1 have been obtained for r_e, ω_e, T_e and D_e, respectively. Owing to the very systematic behavior of the results depending on the basis set and the choice of method, shortcomings of the calculations, such as Rydberg state coupling or insufficient configuration spaces, can be identified independently of experimental data. On the other hand, significant discrepancies with experiment for states which indicate no shortcomings whatsoever in the theoretical treatment suggest the re-evaluation of experimental results. The broad variety of states included in our survey and the uniform quality of the results indicate that the observed systematics is a general feature of the methods and, hence, is molecule-independent.