Exchange and Relativistic Effects on Pi Bonding in the Uranyl Ion

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Abstract
Overlap integrals for the uranyl ion were calculated using Hartree—Fock—Slater and Hartree relativistic U5+ 5f and 6d wavefunctions. Earlier primary overlap calculations by Belford and Belford, using solutions which are approximately Hartree functions, gave π larger than σ overlaps. Exchange effects tend to equalize the σ and π overlaps, and a case was found where the σ overlaps exceed the π values. The relativistic effects are indirect and more pronounced for the 5f orbital. They tend to equalize the σd and πf overlaps, and to increase the πd value which nevertheless remains the largest. These results are indicative of a uranyl structure having strong πd, and weak σf primary bonds, and having at most weak 5f orbital involvement in the secondary bonding. Thus, the overlap results obtained using exchange and relativistically corrected uranium wavefunctions support the view of uranyl complex structures as proposed by Belford and Belford and by Coulson and Lester.

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