A general pseudopotential model for molecules with many valence electrons

Publisher Website
Google Scholar
Abstract
Criteria are discussed for the practical application of ‘valence-electron only’ calculations aimed at simulating ab initio all-electron calculations on molecules containing heavy atoms with many core electrons. A theoretical model is outlined based on the use of pseudopotentials derived from atomic SCF calculations. The model has been used in calculations for NaH, Na2, H2S, S2, H2S2, HCl, Cl2 and NaCl, and has been tested by comparison with reference all-electron calculations. Most of these tests employ double-zeta basis sets and SCF wavefunctions, although polarization functions and complete valence-electron CI wavefunctions have been used in some cases. The model is generally successful for ground-state equilibrium structures, charge distributions and orbital energies.