d Orbitals in positive, neutral, and negative phosphorus atoms

Abstract

SCF calculations using a limited Slater basis set have been carried out for the average value of the most stable term (as selected by Hund's rule) for the s²p², sp³, s²pd, sp²d, and spd², configurations of the positive phosphorus ion, for the s²p³, sp⁴, s²p²d, sp³d, s²pd², sp²d², and spd³ configurations of the neutral phosphorus atom, and for the s²p⁴, sp⁵, s²p³d, sp⁴d, s²p²d², sp³d², s²pd³, and spd⁴ configurations of the negative phosphorus ion. In accord with the literature, it is found that the radii of the 3d orbitals are much smaller when the electronic charge is decreased and when more electrons are promoted to d orbitals. The mean radii are correlated with the orbital energies for the d orbitals and the SCF results are presented for the 13 terms corresponding to the sp²d configuration of the positive phosphorus ion.