Theory of Rydberg Terms of the Nitrogen Molecule

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Abstract
A simplified model is developed for calculation of Rydberg terms and is applied to the three lowest terms of the Worley—Jenkins series in molecular nitrogen. Motion of the excited electron is described by an effective Hamiltonian with interaction terms defined by the core electrons. One-electron energies are obtained relative to a fixed core energy, and the computed terms agree qualitatively with experimental values. The core is described by a minimal set of atomic functions centered at the midpoint of the internuclear axis chosen so that the essential features of charge distribution from the bonding molecular orbitals are reproduced. Rigid requirements of orthogonality between Rydberg and core orbital functions and between Rydberg functions are imposed. Penetration of the Rydberg electron into the core is relatively large and accounts for the major part of δ in the Rydberg formula. It is found that the experimental terms for n=4, 5 are well described by a sum of penetration energy and of the corresponding hydrogenic term, with δ=0.

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