ON THE ASYMPTOTIC-BEHAVIOR OF HARTREE-FOCK ORBITALS

Handy et al. have shown that the asymptotic behavior of Hartree-Fock orbitals is controlled by the energy of highest occupied molecular orbital, except for the atomic case in which only s-orbitals are occupied. However, their proof is not complete at one point. This point is clarified, and a more unified derivation is given. Further, we discuss the preexponential factor r(alpha) of the leading asymptotic term r(alpha) exp[-beta-r], where beta = (-2-epsilon(HOMO)1/2 and epsilon(HOMO) is the orbital energy of HOMO. New results are obtained for linear molecules, and the results of several authors for atoms and non-linear molecules are reproduced.