Combination of pseudopotentials and density functionals

Abstract Semilocal pseudopotentials have been determined for first–row (Li to Ne), second row (Na to Ar), and third‐row atoms (K, Ca). Core–valence correlation is included by adjusting the pseudopotentials to experimental energies of ions with a single valence electron. Correlation within the valence shell is taken into account by using the spin–density functional formalism. The approximations involved in this approach are tested for atomic ionization energies as well as binding energies of monohydrides and alkali diatomics, agreement with experiment is usually satisfactory, but in certain applications density functionals should be already included in the fitting of the local part of the pseudopotential. In addition, 3 s /3 p and 3 s /2 p basis sets (for first and second row, respectively), designed for use in connection with our pseudopotentials, are given; it is shown that they yield reasonable results for both SCF and correlation energies.