Energies and orbital sizes for some Rydberg and valence states of the nitrogen molecule

Accurate SCF computations are reported on the Rydberg states of N₂ of electron configurations $\text{---1π}{}_{\mathrm{u}}{}^3\text{2π}{}_{\mathrm{u}}$, $\text{---1π}{}_{\mathrm{u}}{}^3\text{3σ}{}_{\mathrm{u}}$, and ---3σ_g2π_g, also on the valence states of the configuration $\text{---1π}{}_{\mathrm{u}}{}^3\text{1π}{}_{\mathrm{g}}$. The Rydberg state calculations supplement those of Lefebvre-Brion and Moser. A comparison is made between the $\text{---1π}{}_{\mathrm{u}}{}^3\text{2π}{}_{\mathrm{u}}$ states and the parallel set of states of the $\text{1π}{}_{\mathrm{u}}{}^3\text{1π}{}_{\mathrm{g}}$ configuration. This comparison shows a sharp difference in the ¹Σ⁺ states of the two configurations, the ¹Σ⁺ state being very high in the latter but relatively low in the former configuration. Recknagel coefficients are given for the several states of the two configurations; as expected, these are much smaller for the $\text{1π}{}_{\mathrm{u}}{}^3\text{2π}{}_{\mathrm{u}}$ configuration. Also, the ¹Δ state is relatively lower for the latter configuration.