Energy-adjusted a b i n i t i o pseudopotentials for the rare earth elements

Abstract

Nonrelativistic and quasirelativistic energy‐adjusted ab initio pseudopotentials substituting the 1s–3d core orbitals with corresponding spin–orbit operators for the rare earth elements Ce through Yb have been generated. Excitation and ionization energies from numerical pseudopotential calculations differ by less than 0.1 eV from corresponding numerical all–electron results. The pseudopotentials for Ce have been tested in molecular calculations for the ³Φ ground state of CeO. The derived spectroscopic constants from quasirelativistic pseudopotential CI(SD) calculations including Davidson’s correction (R_e=1.827 Å, D_e=6.95 eV, ω_e=834 cm⁻¹) are in good agreement with experimental values (R_e=1.820 Å, D_e=8.19 eV, ω_e=862 cm⁻¹).