title: Accuracy of relativistic energy-consistent pseudopotentials for superheavy elements 111-118: molecular calibration calculations.
abstract: Relativistic energy-consistent pseudopotentials modelling the Dirac-Coulomb-Breit Hamiltonian with a finite nucleus model for the superheavy elements with nuclear charges 111-118 were calibrated in atomic and molecular calculations against fully relativistic all-electron reference data. Various choices for the adjustment of the f-potentials were investigated and an improved parametrization is recommended. Using the resulting pseudopotentials relativistic all-electron reference data can be reproduced at the self-consistent field level with average absolute (relative) errors of 0.0030 Å (0.15%) for bond lengths and 2.79 N m(-1) (1.26%) for force constants for 24 diatomic test molecules, i.e., neutral or singly charged monohydrides, monofluorides, and monochlorides with closed-shell electronic structure. At the second-order Møller-Plesset perturbation theory level the corresponding average deviations are 0.0033 Å (0.15%) for bond lengths and 2.86 N m(-1) (1.40%) for force constants. Corresponding improved f-potentials were also derived for the pseudopotentials modelling in addition the leading contributions from quantum electrodynamics.
authors: Institute for Theoretical Chemistry, University of Cologne, Greinstr. 4, 50939 Cologne, Germany.
authors: Tim
authors: T
authors: Hangele
authors: Michael
authors: M
authors: Dolg