The fine-structure splitting of the (1 2ΠΩ,ν) levels in Li(1s 22p,2P)Ar and Li(1s 22p,2P)Ne is determined. Analysis of the electronic wave functions demonstrates that the heavy atom contribution to the fine-structure splitting results from the antibonding mixture of valence pπ orbitals on the rare gas and metal atoms. Rydberg orbitals do not contribute significantly to the heavy atom effect.

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