title: Density functionals and transition-metal atoms.
abstract: Density-functional calculations on transition-metal atoms are problematic due to the numerous possible ways, having inequivalent densities, of occupying the d orbitals. The problem is compounded by the issue of real orbitals versus complex orbitals. In this work we systematize the application of density-functional theories to transition-metal atoms using a current-density-dependent functional. For all the single-determinantal angular momentum eigenstates of ground-state terms, we obtain near degeneracy for the energies as we should. Also, we find a simple rule for occupying the real d orbitals that reproduces the energies of the (complex) angular momentum eigenstate results. Thus the long-standing confusion over how to compute transition-metal atom reference energies is resolved.
authors.affiliation: Department of Chemistry, Dalhousie University, Halifax, Nova Scotia B3H 4J3, Canada.
authors.forename: Erin R
authors.initials: ER
authors.lastname: Johnson
authors.forename: Ross M
authors.initials: RM
authors.lastname: Dickson
authors.forename: Axel D
authors.initials: AD
authors.lastname: Becke