A b i n i t i o studies of excited states of polyatomic molecules including spin-orbit and multiplet effects: The electronic states of UF6

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Abstract
The excited electronic states of UF6 between 3–10 eV are investigated by ab initio configuration interaction (CI) calculations using a relativistic effective core potential (RECP) on the uranium and nonrelativistic ECP’s on the fluorines. Spin‐orbit coupling effects are incorporated by diagonalizing an effective one‐electron operator over the CI wave functions. This represents one of the first studies of polyatomic molecules to treat both spin‐orbit effects and multiplet effects arising from electron–electron interactions. A detailed analysis of the electronic states of UF6 is given both with and without spin‐orbit coupling effects. Assignments for the major peaks in the 3–10 eV energy range are given, as aided by recent electron impact studies. Comparisons are made between the present many‐electron states and previous one‐electron theoretical treatments.