Rydberg states of the nitrogen moleculea)

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Abstract
Rydberg states (1,3Σg+, 1,3Σu+, 1,3Πg, and 1,3Πu) of N2 that converge to the N2+ (X 2Σg+) ion have been calculated. The core orbitals are taken as those of the free N2+(X 2Σg+) ion. The Rydberg electron wave functions are expanded by one‐center basis functions which are solution of an electron moving in a sphericalized potential of the N2+(X 2Σg+) ion. This expansion converges rapidly since the basis functions are already a fairly good representation of the Rydberg states especially for the higher ones. The use of one‐center expansion allows us to examine the mixing of the basis functions of different angular‐momentum quantum number l in the Rydberg states which is found to be generally small. Energy levels are reported for singlet and triplet Rydberg states of the Σ and Π types (Λ=0,1) with l from 0–9 and n through 11. The Rydberg levels with l≥4 are entirely hydrogenic. For lower l the quantum defect varies significantly with n within a given l series. Also a wide range of quantum defect is found for different states. Transitions among the various Rydberg series produce a very rich spectrum in the long‐wave infrared region.