INTRACONFIGURATIONAL TRANSITIONS IN TETRAHEDRAL D(2) IONS - ON THE EXPEDIENCY OF THE LIGAND-FIELD MODEL FOR TRANSITION-METAL IONS IN HIGH-OXIDATIONS STATES

被引：14

作者：

ATANASOV, M ^{[1
]}

机构：

[1] BULGARIAN ACAD SCI,INST GEN & INORGAN CHEM,BU-1040 SOFIA,BULGARIA

来源：

CHEMICAL PHYSICS | 1995年 / 195卷 / 1-3期

关键词：

D O I：

10.1016/0301-0104(95)00039-Q

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A ligand field analysis of intraconfigurational transitions in tetrahedral MnO43- and FeO43- is shown to give rather anomalous B values for the ground state configuration e(2). A model taking explicit account of interactions between d(2) (ionic) multiplets and singly excited (ligand to metal) charge transfer configurations is used to show that for low charge transfer energies each state of e(2) is modified to a different extent by covalency effects. A full account of all possible charge transfer excitations in comparison with published spectral data allows to deduce a rather important electrostatic component to the multiplet splittings originating from the e(1)t(2)(1) (strong field) configuration. This is drawn as an explanation for the considerable success of the ligand field model in describing term energies belonging to such a configuration.

引用

页码：49 / 58

页数：10

共 32 条

[1]

Milstein, Holt, Inorg. Chem., 8, (1969)

[2]

Milstein, Ackerman, Holt, McGarvey, Electronic structures of chromium(V) and manganese(V) in phosphate and vanadate hosts, Inorganic Chemistry, 11, (1972)

[3]

Borromei, Oleary, Day, J. Chem. Soc. Faraday Trans., 73, (1977)

[4]

Borromei, Oleary, Day, J. Chem. Soc. Faraday Trans., 77, (1981)

[5]

Reinen, Lachwa, Allman, Z. Anorg. Allg. Chem., 71, (1986)

[6]

Lachwa, Reinen, Inorg. Chem., 28, (1989)

[7]

Oetliker, Herren, Gudel, Kesper, Albrecht, Reinen, J. Chem. Phys., 100, (1994)

[8]

DiSipio, DeMichelis, Baiocchi, Ingletto, Electronic absorption spectra of tetrahedral oxoanions: Ferrate(VI) ion, Transition Metal Chemistry, 5, (1980)

[9]

Herren, Gudel, Inorg. Chem., 31, (1992)

[10]

Brunold, Hauser, Gudel, J. Luminescence, 59, (1994)

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