All-electron molecular Dirac–Hartree–Fock calculations: Properties of the group IV monoxides GeO, SnO, and PbO

Abstract

Dirac–Hartree–Fock calculations have been carried out on the electronic ground states of the group IV monoxides GeO, SnO, and PbO. Geometries, dipole moments, and infrared data are presented. For comparison, nonrelativistic, first-order perturbation and relativistic effective core potential calculations have also been carried out. Where appropriate, the results are compared with the experimental data and previous calculations. Spin–orbit effects are of great importance for PbO, where first-order perturbation theory including only the mass–velocity and Darwin terms is inadequate to predict the relativistic corrections to the properties. The relativistic effective core potential results show a larger deviation from the all-electron values than for the hydrides and confirm the conclusions drawn on the basis of the hydride calculations.