Density-functional investigation of bonding in tetrahedral MO4 anions

被引：50

作者：

Bridgeman, AJ ^{[1
]}

Cavigliasso, G

机构：

[1] Univ Hull, Dept Chem, Kingston Upon Hull HU6 7RX, Yorks, England

[2] Univ Cambridge, Dept Chem, Cambridge CB2 1EW, England

来源：

POLYHEDRON | 2001年 / 20卷 / 18期

基金：

英国工程与自然科学研究理事会;

关键词：

main group; transition metals; oxoanions; bonding; density-functional theory;

D O I：

10.1016/S0277-5387(01)00772-0

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The structure and bonding in main-group and transition-metal oxoanions with MO4 stoichiometry have been investigated by density-functional methods. Nine main-group (SiO44-, PO43-, SO42-, ClO4-, GeO44-, AsO43-, SeO42-, BrO4-, IO4-) and ten transition-metal (TiO44-, VO43-, CrO42-, MnO4-, NbO43-, MoO42-, TcO4-, TaO43-, WO42-, ReO4-) oxoanions have been studied. For most species, the optimized geometry of the isolated molecule satisfactorily reproduces the experimental structural parameters in the crystalline phase. Mulliken charges have been calculated, and have been found to be, in all cases, significantly smaller than the formal oxidation states. Mayer bond-order indexes and the composition of the Kohn-Sham orbitals have been utilized for the analysis of bonding in the oxoanions. The former reveal some M-O multiple-bonding character in all MO, systems, and are in good agreement with values determined from classical bond-valence analysis. The molecular-orbital analysis indicates that the chemical bonds possess Msp and Osp character in the main-group species, and Md and Op character in the transition-metal systems. (C) 2001 Elsevier Science Ltd. All rights reserved.

引用

页码：2269 / 2277

页数：9

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