Ab initio effective core potentials for molecular calculations. Potentials for main group elements Na to Bi

Abstract

A consistent set of ab initio effective core potentials (ECP) has been generated for the main group elements from Na to Bi using the procedure originally developed by Kahn. The ECP’s are derived from all-electron numerical Hartree–Fock atomic wave functions and fit to analytical representations for use in molecular calculations. For Rb to Bi the ECP’s are generated from the relativistic Hartree–Fock atomic wave functions of Cowan which incorporate the Darwin and mass–velocity terms. Energy-optimized valence basis sets of (3s3p) primitive Gaussians are presented for use with the ECP’s. Comparisons between all-electron and valence-electron ECP calculations are presented for NaF, NaCl, Cl2, Cl2−, Br2, Br2−, and Xe2+. The results show that the average errors introduced by the ECP’s are generally only a few percent.