化学
镧系元素
价(化学)
分子轨道
结合能
谱线
电子结构
原子轨道
金属
电子组态
X射线光电子能谱
多重态
光电发射光谱学
原子物理学
结晶学
计算化学
分子
有机化学
核磁共振
电子
离子
物理
天文
量子力学
作者
Yurii A. Teterin,A. Yu. Teterin
出处
期刊:Russian Chemical Reviews
[Turpion]
日期:2002-05-31
卷期号:71 (5): 347-381
被引量:139
标识
DOI:10.1070/rc2002v071n05abeh000717
摘要
The results of the X-ray photoelectron spectroscopy studies of the electronic structures of trifluorides, oxides and other compounds of Sc, Y and lanthanides (Ln) from La to Lu, except for Pm, in the binding energy range from 0 to 1350 eV are generalised. The established dependences of the Ln4f binding energies and the relative intensities of lines on the atomic number Z do not contradict the theoretical data stating that the Ln4f atomic orbitals (AO) participate markedly in the formation of molecular orbitals (MO) in the lanthanide compounds. It is established that inner valence molecular orbitals (IVMO) composed of the metal Sc3p, Y4p, Ln5p AO and the ligand L(O,F)2s AO are formed in these systems in addition to the outer valence molecular orbitals (OVMO). It is shown that the spectral fine structure caused by multiplet splitting, many-body perturbation and dynamic effects is correlated with the lanthanide oxidation state, the spin state of ions and the mechanisms of the secondary electronic processes accompanying the photoemission and can serve as a characteristic for identification of lanthanide compounds. Charge induction is discussed using titanium and niobium double oxides as examples. The bibliography includes 206 references.
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