Relations between Rydberg-valence interactions in the O_2 molecule

摘要

Using a single-configuration formulation, analytical expressions are derived for the (X fl~) nso-~. flp 7Th. and 0P~u Rx’dberg-valence interaction matrix elements in 02. In addition, new results from diabatic, coupled-channel deperturbations of experimental data dependent on these inter~uon~ 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 np i~ 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 nplTu Rydberg states which have yet to be observed.