Overlap-matched atomic orbitals

Abstract

Single Slater-type orbitals can be determined which reproduce overlap integrals calculated using self-consistent-field atomic orbitals expressed in an extended basis set. Requirements and procedures for determining orbital parameters adequate for the chemically important range of internuclear distances are developed and applied to the more familiar elements. This method is applicable even in cases where no single exponential function is a generally good representation of the shape of the atomic orbital, such as the 3d function for a transition metal ion.