Electronic structure and the x-ray and photoelectron spectra of hexacyano-complexes of Fe(II) and Fe(III) in the cluster approximation by the SCF-Xα-SW method

Quantum-chemical calculations of the electronic structure of the hexacyano-complexes [Fe(CN)6]4- and [Fe(CN)6]3- have been carried out by the SCF-Xα-SW method in the cluster approximation, and their photoelectron and x-ray emission and absorption spectra constructed. The contribution of the resonance emission to the x-ray emission spectra, and the energy position of the satellite lines of many-electron character in the FeLα spectra, have been calculated. The fine structure of the spectra has been interpreted on the basis of a detailed comparison of the theoretical and experimental results, and it has been concluded that spin polarization has little influence on the photoelectron and x-ray spectra of the Fe(III) complex