Electron correlation energy in confined two-electron systems

Abstract

Radial, angular and total correlation energies are calculated for four two-electron systems with atomic numbers Z = 0 – 3 confined within an impenetrable sphere of radius R. We report accurate results for the non-relativistic, restricted Hartree–Fock and radial limit energies over a range of confinement radii from 0.05 – 10 a 0 . At small R, the correlation energies approach limiting values that are independent of Z while at intermediate R, systems with Z ⩾ 1 exhibit a characteristic maximum in the correlation energy resulting from an increase in the angular correlation energy which is offset by a decrease in the radial correlation energy.