d Orbitals in the Excited Sulfur Atom

Sulfur 3d orbitals in the sp3d2 configuration are represented by a two-term Slater wavefunction. The energies of the 7F, 7P, 5H, 3I, 1I, and one of the 1S terms are minimized with respect to the two wavefunction exponents and the mixing coefficient. The core wavefunction is the same throughout. In the deeper terms the d orbitals have mean radii upwards from 1.85 Å (7F). In the highest term considered, the mean radius is 2.65 Å (1S). In a single-configuration valence state the mean radius is at 2.39 Å, and in the (multiconfiguration) valence state for equivalent octahedral hybrids it is 1.67 Å.