Electronic Structure of the α and β Isomers Of [Mo8O26]4-
- 4 June 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 41 (13) , 3500-3507
- https://doi.org/10.1021/ic0255510
Abstract
The structure and bonding in α and β octamolybdate anions have been investigated using density functional methods. In general, good computational−experimental agreement for the geometrical parameters has been obtained. The electronic structure of the anions has been probed with molecular orbital and Mulliken−Mayer methods. All Mo−O interactions have been found to be predominantly d(Mo)−p(O) in character. Several multicentered molecular orbitals can be described as σ or π closed-loop structures, but the proposed connection with the stability of the polyanions is not completely supported by the calculations. Mayer indexes correspond to fractional multiple character for terminal bonds and approximately single or low-order character for bridging bonds, in accordance with structural and bond valence results. The valency analysis has yielded similar overall bonding capacity for the various oxygen atoms. A distribution of the negative charge over all types of oxygen sites and metal charges considerably smaller than the formal oxidation states have been obtained from the Mulliken analysis.Keywords
This publication has 33 references indexed in Scilit:
- Bonding and charge distribution in isopolyoxometalate ions and relevant oxides—A bond valence approachPublished by Springer Nature ,2007
- A bond model for polyoxometalate ions composed of MO6 octahedra (MOk polyhedra with k>4)Published by Springer Nature ,2007
- Electronic structure of Mo and W [M7O24]6– isopolyanionsJ. Chem. Soc., Dalton Trans., 2002
- Molecular and electronic structures of six-coordinate chloro-oxo-metalate complexes of V, Nb, Ta, Mo, and WJ. Chem. Soc., Dalton Trans., 2001
- Structure and Bonding in Dinuclear Oxoanions of V, Nb, Ta, Mo, and WThe Journal of Physical Chemistry A, 2001
- Chemistry with ADFJournal of Computational Chemistry, 2001
- Bonding in the trihalides (X3−), mixed trihalides (X2Y−) and hydrogen bihalides (X2H−). The connection between hypervalent, electron-rich three-center, donor–acceptor and strong hydrogen bonding ‡J. Chem. Soc., Dalton Trans., 1997
- Chemical applications of topology and group theory. 25. Electron delocalization in early-transition-metal heteropoly- and isopolyoxometalatesInorganic Chemistry, 1991
- Quantum-chemical definition of the atomic valence in molecules and crystalsTheoretical Chemistry Accounts, 1991
- Self-Consistent Equations Including Exchange and Correlation EffectsPhysical Review B, 1965