Relations between Rydberg-valence interactions in the O₂ molecule

Abstract

Using a single-configuration formulation, analytical expressions are derived for the (X²Πg) 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 npπuRydberg 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 ¹Σ−uRydberg states which have yet to be observed. Show more