HARTREE–FOCK WAVE FUNCTIONS FOR EXCITED STATES: THE 2 1S STATE OF HELIUM

Abstract
Hartree–Fock wave functions for the first-excited singlet states of several members of the helium isoelectronic sequence have been calculated. It is shown that unphysically low energies result if the excited-state function is not constrained to be orthogonal to the ground-state eigenfunction, and the excited-state orbitals are chosen orthogonal.If the excited-state orbitals are not chosen orthogonal, the effect of the overall constraint is small, raising the total energy very slightly; however, the effect of imposing both constraints simultaneously is appreciable. It is concluded that the most satisfactory approximation involves nonorthogonal excited-state orbitals, together with an overall orthogonality constraint towards the ground state.

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