Valence Electron Studies with Gaussian-Based Model Potentials and Gaussian Basis Functions. I. General Discussion and Applications to the Lowest s and p States of Li and Na

Abstract

A new model potential for one-valence-electron atoms is introduced. It consists [Eq. (6)] of a core Coulomb potential modified by the addition of a Gaussian screened Coulomb potential. This potential has the desired features outlined for a model potential, and it has particularly convenient and simple mathematical properties when used with Gaussian basis functions. Since the smooth valence orbitals are sought, Gaussian functions are a good basis set because their deficiencies in nuclear regions do not enter the problem. The potential is calibrated to experimental energies for the 2s and 2p states of Li and 3s and 3p states of Na, using extended basis sets. The model Hamiltonians so defined are used with a variety of more modest basis sets to determine pseudowavefunctions. Based on comparisons with ab initio orbitals, energy analyses, radial density calculations, and overlap and expectation value calculations, the conclusion is that good valence pseudowavefunctions can be obtained by this approach with relatively small basis sets. The approach looks promising for valence-only molecular studies.