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

The present study of cyano complexes leads to the following conclusions.

1.	The x-ray and PE spectra are directly related to the results of quantum-chemical calculations: the IP and the partial charges or populations. Thus the complete set of theoretical x-ray and PE spectra apparently represents one of the most successful ways of obtaining a clear graphical representation of the results of quantum-chemical calculations.
2.	The complete set of x-ray and PE spectra provide a good test for verifying quantum-chemical theory, for selecting a model of the electronic structure, and for refining the procedure for carrying out the calculations, in the present case of the X-SW method the method for selecting the radii of the atomic spheres.
3.	With the optimum selection of the radii of the atomic spheres, the X-SW method describes with satisfactory accuracy those aspects of the electronic structure of coordination compounds that are reflected in the x-ray (except the XE K5 spectra) and PE spectra of the valence orbitals.

Institute of Inorganic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 29, No. 3, pp. 53–63, May–June, 1988.