X-ray spectroscopic studies of the electronic structural of transition-metal complex compounds

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The purpose of this project is to show the X-ray Kalpha, Kbeta and Lbeta_<2,15> emission spectra from transition-metal complex compounds and various metal compounds along with the X-ray K and L absorption spectra reported previously and to obtain information on their electronic structures. The results obtained are as follows:A. The FWHM of the F Kalpha_<1,2> emission bands of 3d transition-metal fluorides MF_2 (M = Mn, Fe, Co, Ni, Cu, Zn) is closely related to the difference in electro negativity between the metal and fluorine atoms. The structures at the F K absorption edges are interpreted in terms of a molecular orbital model.B. The S Kbeta emission and S K absorption-edge spectra of TiS_2, ZrS_2 and HfS_2 are compared with theoretical DOS cures of these compounds. There is good agreement between them. The relative intensities of absorption peaks at the K edges depend on the degree of covalent mixing of the metal d and sulfur 3p states.C. The Pd Lbeta_<2,15> emission spectra of PdCl_2, Pd(ac)_2 and Pd(acac)_2 consist of a prominent peak with a high-energy structure and are alike, in contrast to the case of the Pd L_<III> absorption spectra of these compounds reported previously. The Pd Lbeta_<2,15> emission, Pd L_<III> absorption, Cl Kbeta emission and Cl K absorption spectra of PdCl_2 are interpreted in terms of the MOs of square-planar complex [PdCl_4]^<2->.D. Chemical shifts are observed for the Ca^<2+> Kalpha_<1,2>, Kbeta_<1,3> and Kbeta_5 emission peaks of CaF_2, CaO and CaS. The Kbeta_5 bands are attributed to the cross transition from the anion p-like valence band to the Ca^<2+> 1s level.