Knowledge Bank

“In the calculation of the total molecular energy, the direct relativistic correction can be comparable to the correlation energy even for Z’s of the Order of ten. Nor should it ho assumed that relativistic effects cancel in energy difference calculations, except when no changes occur in the inner shells. A recent comparison of non-relativistic (NR) and relativistic (R) Hartree calculations for normal uranium by Boyd, Larson, and $Waher1$ shows that the valence orbitals in the (R) case are more diffuse, due to more effective shielding of the nuclear charge by the more tightly bound inner orbitals. This indirect relativistic effect is more pronounced for the 5f than for the 6d orbital. The consequences of such efforts in the uranyl $(UO2++)$ electronic structure and on the between uranyl and nitrato groups in the uranyl-trinitrato complex have been investigated. Wave-forms and overlaps in the (NR) and (R) cases will be shown and their significance in these uranyl problems discussed.”