Spin-orbit configuration interaction calculations of electronic spectra of RuO2+ and OsO2+ catalytic cores

TitleSpin-orbit configuration interaction calculations of electronic spectra of RuO2+ and OsO2+ catalytic cores
Publication TypeConference Paper
Year of Publication2012
AuthorsErmler, W., J. Tilson, and R. J. Fowler
Conference NameSouthwest Regional Meeting of the American Chemical Society (SWRMACS 2012)
Conference LocationBaton Rouge, LA
Abstract

Low-lying potential energy curves of RuO2+ and OsO2+ catalytic core molecules are analyzed using large-scale spin-orbit configuration interaction (SOCI) calculations based on multireference molecular wavefunctions. Relativistic effects are included using effective core potentials. The large spin-orbit splitting energies of the 4d and 5d subshells of Ru and Os require that the spin-orbit coupling operator be included when calculating the electronic spectra. The ground states of both molecules are triply bonded systems of 0+(1Σ+) symmetry having bond lengths, harmonic frequencies and dissociation energies of 1.63 and 1.70 Å, 757 and 772 cm-1, and 83.8 and 97.2 kcal/mol, respectively. These results are consistent with experimental observation that the ground state of complexed RuO2+ is diamagnetic.