|Title||Spin-orbit configuration interaction calculations of electronic spectra of RuO2+ and OsO2+ catalytic cores|
|Publication Type||Conference Paper|
|Year of Publication||2012|
|Authors||Ermler, W., J. Tilson, and R. J. Fowler|
|Conference Name||Southwest Regional Meeting of the American Chemical Society (SWRMACS 2012)|
|Conference Location||Baton Rouge, LA|
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.