Valence ionization spectra of group six metal hexacarbonyls studied by the symmetry-adapted cluster-configuration interaction method

摘要

The valence ionization spectra up to 20 eV of group six metal carbonyls, chromium hexacarbonyl, molybdenum hexacarbonyl, and tungsten hexacarbonyl were studied by the symmetry-adapted cluster-configuration interaction SAC-CI method. The assignments of the spectra are given based on reliable SAC-CI calculations. The relativistic effects including the spin-orbit effects are important for the ionization spectrum of WCO6. The relation between the metal-CO distance and ionization energies was examined. The lowest ionization energies of the three metal carbonyls are approximately the same because of the energy dependence of the metal-CO length and relativistic effects. In CrCO6, the Cr–CO interaction significantly increases the lowest ionization energy in comparison with MoCO6 and WCO6 because of the relatively short metal-CO bond length. The relativistic effect reduces the lowest ionization energy of WCO6 because the effective core potential of 5d electrons is more efficiently screened as a result of the relativistic contraction of the inner electrons.