Orbital modification by the coulomb field of ligand atoms of later second-row elements in perfect pairing valence states

Abstract

The effect of the electrostatic field of ligand atoms on the size of 3d orbitals and the energetics of the valence state of the second-row atoms in SF₆, PF₅, HPF₄, H₂PF₃, and CIF₃ has been studied by use of multiconfigurational or perfect-pairing valence states. 3d Orbitals have in all cases been shown to be contracted in the presence of electronegative ligands. The contribution of 3d orbitals to the interatomic energy has been shown to be important. The use of two-term radial wave-functions, the neglect of intra- and inter-atomic exchange, and the alternative use of single-configurational valence states are discussed.