Energy-consistent pseudopotentials for group 11 and 12 atoms: adjustment to multi-configuration Dirac–Hartree–Fock data

TLDR: In this article, two-component relativistic pseudopotentials (i.e., scalar-relativistic and spin-orbit (SO) potentials) of the energy-consistent variety have been adjusted for the group 11 and 12 atoms Cu, Zn, Ag, Cd, Au, Hg, replacing the 1s−2p, 1s-3d, 1 s−3d and 1s −4f cores, respectively.

Abstract: Two-component relativistic pseudopotentials (i.e., scalar-relativistic and spin–orbit (SO) potentials) of the energy-consistent variety have been adjusted for the group 11 and 12 atoms Cu, Zn; Ag, Cd; Au, Hg, replacing the 1s–2p; 1s–3d; and 1s–4f cores, respectively. The adjustment has been done for the valence-energy spectrum of (near-)neutral atoms, to reference data from numerical all-electron four-component multi-configuration Dirac–Hartree–Fock (MCDHF) calculations, including the two-electron Breit interaction. For use in molecular calculations, the potentials have been supplemented by energy-optimized (12s12p9d3f2g)/[6s6p4d3f2g] valence basis sets. First benchmark applications of the potentials and basis sets are presented for atomic excitation energies and SO splittings at a correlated level, and for ground and excited state spectroscopic properties of group 11 monohalides and group 12 dimers.