Relations between Rydberg-valence interactions in the O2 molecule

Using a single-configuration formulation, analytical expressions are derived for the (X 2Πg) nsσg, npπu, and npσu Rydberg-valence interaction matrix elements in O2. In addition, new results from diabatic, coupled-channel deperturbations of experimental data dependent on these interactions are reported for n=3 and 4. Using these results, the large differences in magnitude between the Rydberg-valence couplings for the constituent states of the npπu Rydberg complex that are predicted by the analytical expressions are verified experimentally. Effective values for several two-electron integrals are obtained semiempirically through comparison between analytical expressions and deperturbed experimental values for the Rydberg-state energies and Rydberg-valence couplings, allowing predictions to be made for the spectroscopy of the npπu 1Σu− Rydberg states which have yet to be observed.