The orthogonality assumption in the Hartree–Fock approximation for 2pn3p configurations

Abstract

Hartree–Fock (HF) results for Na+ 2p53p1S and Ne+ 1s2p53p2S are reported. In order for the SCF process to converge, additional orthogonality constraints to the corresponding 2p6 states had to be introduced. The resulting 2p functions were nodeless. Similar calculations were performed for O 2p33p2P and Ne+ 2p43p2P for which standard HF results were available. A comparison of the two methods indicates that, unlike the He 1s2s1S case, the additional orthogonality constraint did not improve the total energy although it removed the extra node from the 2p function.