Matrix Hartree–Fock calculations are reported for 3d transition metals in a configuration chosen to represent, as closely as is possible with integral occupation numbers, an atom in an fcc metal. The cubic symmetry shell (3dt)6 is assumed to be fully occupied, and electrons are successively removed from the (3de)4 shell to represent atoms from Cu to Mn. A single 4s orbital is included, with independent calculations for the two possible choices of relative spin of the 4s orbital and 3de shell. Orbital energies are computed for each of the nonequivalent 4s and 3d orbitals, and the relationship of these quantities with transition metal energy bands is discussed. Intra‐atomic orbital energy splittings are found to be comparable in magnitude to energy band splittings. Radial densities of the 4sα and 4sβ orbitals are computed. These densities are found to be compatible with a proposed explanation of recently observed negative magnetization regions within the unit cell of ferromagnetic transition metals. Copyright © 1967 John Wiley & Sons, Inc.