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

本项目的目的是展示过渡金属配合物和各种金属化合物的X射线Ka、Kbeta和Lbeta_<2，15>发射光谱，以及之前报道的X射线K和L吸收光谱，并获得有关它们的电子结构的信息。沿着。所得结果如下：A. 3d过渡金属氟化物MF_2（M = Mn，Fe，Co，Ni，Cu，Zn）的F K α <1，2>发射带的半高宽与金属原子和氟原子的电负性差密切相关。用分子轨道模型解释了F-K吸收边的结构。本文比较了TiS_2，ZrS_2和HfS_2的S K β发射谱和S K吸收边谱与理论DOS曲线。他们之间有很好的协议。K边吸收峰的相对强度取决于金属d和硫3 p态的共价混合程度。PdCl_2、Pd（ac）_2和Pd（acac）_2的PdL β_（2，15）发射光谱由一个具有高能结构的突出峰组成，与<III>文献报道的这些化合物的PdL_（2，15）吸收光谱不同，它们具有相似的结构。本文<III>用平面正方形配合物[PdCl_4]^的分子轨道解释了PdCl_2的PdL β_（2，15）发射、PdL_（2，15）吸收、Cl K β发射和Cl K吸收光谱<2->。对CaF_2、CaO和CaS的Ca^&lt;2+&gt; K α_（1，2）、K β_（1，3）和K β_（5）发射峰进行了化学位移测量。Kbeta_5带是由类p阴离子价带到Ca^&lt;2+&gt; 1 s能级的交叉跃迁。

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.