title: Energy-consistent relativistic pseudopotentials and correlation consistent basis sets for the 4d elements Y-Pd.
abstract: Scalar-relativistic pseudopotentials and corresponding spin-orbit potentials of the energy-consistent variety have been adjusted for the simulation of the [Ar]3d(10) cores of the 4d transition metal elements Y-Pd. These potentials have been determined in a one-step procedure using numerical two-component calculations so as to reproduce atomic valence spectra from four-component all-electron calculations. The latter have been performed at the multi-configuration Dirac-Hartree-Fock level, using the Dirac-Coulomb Hamiltonian and perturbatively including the Breit interaction. The derived pseudopotentials reproduce the all-electron reference data with an average accuracy of 0.03 eV for configurational averages over nonrelativistic orbital configurations and 0.1 eV for individual relativistic states. Basis sets following a correlation consistent prescription have also been developed to accompany the new pseudopotentials. These range in size from cc-pVDZ-PP to cc-pV5Z-PP and also include sets for 4s4p correlation (cc-pwCVDZ-PP through cc-pwCV5Z-PP), as well as those with extra diffuse functions (aug-cc-pVDZ-PP, etc.). In order to accurately assess the impact of the pseudopotential approximation, all-electron basis sets of triple-zeta quality have also been developed using the Douglas-Kroll-Hess Hamiltonian (cc-pVTZ-DK, cc-pwCVTZ-DK, and aug-cc-pVTZ-DK). Benchmark calculations of atomic ionization potentials and 4d(m-2)5s(2)-->4d(m-1)5s(1) electronic excitation energies are reported at the coupled cluster level of theory with extrapolations to the complete basis set limit.
authors.affiliation: Department of Chemistry, Washington State University, Pullman, Washington 99164-4630, USA. kipeters@wsu.edu
authors.forename: Kirk A
authors.initials: KA
authors.lastname: Peterson
authors.forename: Detlev
authors.initials: D
authors.lastname: Figgen
authors.forename: Michael
authors.initials: M
authors.lastname: Dolg
authors.forename: Hermann
authors.initials: H
authors.lastname: Stoll