EXCITED AND IONIZED STATES OF RUO4 AND OSO4 STUDIED BY SAC AND SAC-CI THEORIES

The excitation and ionization spectra of RuO4 and OsO4 are studied theoretically by the symmetry-adapted cluster (SAC) and SAC-CI theories. This is the attempt to assign whole of the spectra by ab initio claculations including electron correlations. In the ground state, electron correlations work to reduce the polarity of the M-O bond overestimated in the Hartree-Fock calculation. The OS-O bond is stronger than is the Ru-O bond, which is reflected in the differences of the excitation and ionization spectra of RuO4 and OsO4. The excitation energies of the experimental spectra are well reproduced by the SAC-CI theory, though the calculated intensities of some peaks are very small in comparison with the experiments. The outer-valence ionization spectra calculated by the SAC-CI theory agree well with the experimental photoelectron spectra. Some shake-up peaks that are accompanied with an electron-transfers from oxygen to metal are also calculated.