Self-Consistent Molecular-Orbital Methods. I. Use of Gaussian Expansions of Slater-Type Atomic Orbitals

TLDR

These Gaussian‑type expansions share common exponents between Slater‑type 2s and 2p functions. The study presents least‑squares representations of Slater‑type atomic orbitals as sums of Gaussian‑type orbitals and proposes a standard set of ζ values for molecular calculations. Using these orbitals in self‑consistent molecular‑orbital calculations yields rapidly converging atomization energies, atomic populations, and dipole moments, with ζ exponents largely independent of Gaussian count, and the suggested standard ζ set performs well for total and atomization energies but not for charge distribution.

Abstract

Least-squares representations of Slater-type atomic orbitals as a sum of Gaussian-type orbitals are presented. These have the special feature that common Gaussian exponents are shared between Slater-type 2s and 2p functions. Use of these atomic orbitals in self-consistent molecular-orbital calculations is shown to lead to values of atomization energies, atomic populations, and electric dipole moments which converge rapidly (with increasing size of Gaussian expansion) to the values appropriate for pure Slater-type orbitals. The ζ exponents (or scale factors) for the atomic orbitals which are optimized for a number of molecules are also shown to be nearly independent of the number of Gaussian functions. A standard set of ζ values for use in molecular calculations is suggested on the basis of this study and is shown to be adequate for the calculation of total and atomization energies, but less appropriate for studies of charge distribution.