Estimating the Hartree—Fock limit from finite basis set calculations

Abstract

It is demonstrated that the polarization-consistent basis sets, which are optimized for density functional methods, are also suitable for Hartree–Fock calculations, and can be used for estimating the Hartree–Fock basis set limit to within a few micro-hartree accuracy. Various two- and three-point extrapolation schemes are tested and exponential functions are found to be superior compared to functions depending on the inverse power of the highest angular momentum function in the basis set. Total energies can be improved by roughly an order of magnitude, but atomization energies are only marginally improved by extrapolation.