An expansion method for calculating atomic properties VII. The correlation energies of the lithium sequence

Abstract If the energy of an atomic system is expanded in inverse powers of the nuclear charge Z, the leading term of the correlation energy after degeneracies have been removed is a constant which can be expressed as a weighted sum of electron pair energies and certain non-additive terms. The pair energies may be obtained from direct two-electron variational calculations and the non-additive terms may be evaluated exactly. Calculations are carried out for the lithium 2S sequence with the result that the non-relativistic eigenvalues are given by E(Z) = − 1.125Z2 + 1.02280521Z−0.40814899 + O(Z-1).