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We report the results of multiple scattered wave SCF X‐alpha calculations of the one‐electron cross section for K‐shell photoabsorption in the molecular complexes MoO₄⁻⁻, CrO₄⁻⁻, and MoS₄⁻⁻. We show that the method can successfully account for energy separations and relative cross sections of spectral features both below and above the K‐shell ionization threshold. Furthermore, we show: (a) that the first fairly intense peak on the low energy side of the rising edge for molybdate and chromate is due to a dipole allowed transition to a bound antibonding state of mainly nd character on the metal ion; this transition is possible because of the mixing with the ligand p orbitals having the proper T₂ symmetry induced by the tetrahedral molecular potential; (b) the shoulder on the rising absorption edge can be explained by the beginning of the steplike continuum absorption when convolved with a Lorentzian function of …