Calculation of Rydberg Levels in the Nitrogen Molecule

Abstract

The energy levels of the lowest members of Rydberg series in N₂ have been calculated using LCAO—MO—SCF functions. We have found only one ¹Σ_u⁺ level around 104 000 cm⁻¹ and this is the first member of a Rydberg series which converges to the X ²Σ_g⁺ ground state of N₂⁺. This level can be identified with the p′ ¹Σ_u⁺ state. Our calculations suggest that, if the Worley—Jenkins Rydberg states have ¹Σ_u⁺ symmetry (which is not yet absolutely definite) then, no Rydberg series of the type (npπ_u) ¹II_u←X¹Σ_g⁺ have yet been observed. Our calculations confirm the configurations previously suggested for the upper states of Worley's third and Hopfield's Rydberg series. The states D ³Σ_u⁺, E ³Σ_g⁺, z ¹Δ_g, x ¹Σ_g⁻, and y ¹II_g are shown to be the first members of Rydberg series.