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

Key Points

• To generate and validate nonrelativistic and quasirelativistic energy-adjusted ab initio pseudopotentials for the rare earth elements cerium through ytterbium.
• Generated pseudopotentials replacing the 1s–3d core orbitals with corresponding spin–orbit operators for elements Ce through Yb.
• Evaluated atomic excitation and ionization energies against numerical all-electron reference calculations.
• Tested cerium pseudopotentials in molecular CI(SD) calculations including Davidson's correction for the 3Φ ground state of CeO.
• Atomic excitation and ionization energies calculated with numerical pseudopotentials deviated from all-electron calculations by less than 0.1 eV.
• CeO molecular calculations yielded spectroscopic constants of Re=1.827 Å, De=6.95 eV, and ωe=834 cm−1, closely aligning with experimental values (Re=1.820 Å, De=8.19 eV, ωe=862 cm−1).