Charge renormalization at the large-D limit for atoms and molecules

Abstract

By combining Hartree–Fock results for nonrelativistic ground-state energies of atoms and molecules with analytic expressions for the large-dimensional limit of atoms, we obtained a simple systematic renormalization procedure. This procedure is based on the variation of the nuclear charges, {Zi}, and internuclear distances, {Rij}, of the Hartree–Fock Hamiltonian such that the Hartree–Fock energy will be significantly closer to the exact energy. We calculate to first order in δZ the leading contribution to the correlation energy by changing the nuclear charge to some renormalized nuclear charge, Z + δZ. Our goal is to find the parameter δZ in a completely self-consistent and systematic manner, which we accomplish by utilizing the analytically known solutions for both the exact and Hartree–Fock energies for all atoms in the large-D limit. We demonstrate that use of the dimensional renormalization parameter δZ∞. Directly in standard Hartree–Fock calculations for atoms and homonuclear and heteronuclear molecules yields about 2/3 or more of the correlation energy. © 1995 John Wiley & Sons, Inc.