A b i n i t i o studies of AuH, AuCl, HgH and HgCl2 using relativistic effective core potentials

Relativistic effective core potentials (ECP) are derived for Au and Hg atoms, where the ECP incorporates the Coulomb and exchange contributions of the core orbitals, the core-orthogonality terms for the valence orthogonality terms for the valence orbitals, and the effect of the ’’mass–velocity’’ and ’’Darwin’’ relativistic effects on the valence orbitals. The results of atomic valence-electron (VE) calculations with the ECP’s compare favorably with relativistic Hartree–Fock and Dirac–Hartree–Fock calculations and with experiment, when the effects of spin–orbit coupling are included in the VE calculations. Nonrelativistic calculations, by contrast, lead to erroneous predictions and to differences in excitation energies of 1.5–3.5 eV. The large relativistic effects in the atoms carry over into the AuH, AuCl, and HgCl2 molecules, as they are important in determining correct bond lengths and bond energies and in influencing the charge distributions. Similarly large relativistic effects are encountered in ionization potentials calculated for HgCl2 from orbital energies and from SCF calculations. Spin–orbit coupling is introduced to compare with the experimental photoelectron spectrum. An extensive study of the lowest electronic states of HgH is presented, where the effects of spin–orbit coupling are critical in describing the potential energy curves of the excited 2Π1/2 and 22Σ+1/2 states.