CHARGE RENORMALIZATION AT THE LARGE-D LIMIT FOR ATOMS AND MOLECULES

By combining Hartree-Fock results for nonrelativistic ground-state ene rgies of atoms and molecules with analytic expressions for the large-d imensional limit of atoms, we obtained a simple systematic renormaliza tion procedure. This procedure is based on the variation of the nuclea r charges, (Z(i)), and internuclear distances, (R(ij)), of the Hartree -Fock Hamiltonian such that the Hartree-Fock energy will be significan tly closer to the exact energy. We calculate to first order in delta Z the leading contribution to the correlation energy by changing the nu clear charge to some renormalized nuclear charge, Z + delta Z. Our goa l is to find the parameter delta Z 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 a toms in the large-D Limit. We demonstrate that use of the dimensional renormalization parameter delta Z(infinity) directly in standard Hartr ee-Fock calculations for atoms and homonuclear and heteronuclear molec ules yields about 2/3 or more of the correlation energy. (C) John Wile y & Sons, Inc.