Molecular and Electronic Structures of M2O7 (M = Mn, Tc, Re)
| Autor: | Alfred P. Sattelberger, Bradley C. Childs, Frederic Poineau, Paul M. Forster, Keith V. Lawler, Kenneth R. Czerwinski, Daniel S. Mast |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
Chemistry
Molecular orbital diagram 02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology Pi bond 01 natural sciences Bond order 0104 chemical sciences Inorganic Chemistry Bond length Crystallography Chemical bond Sextuple bond Single bond Physical and Theoretical Chemistry Bond energy 0210 nano-technology |
| Zdroj: | Inorganic Chemistry. 56:2448-2458 |
| ISSN: | 1520-510X 0020-1669 |
| Popis: | The molecular and electronic structures of the group 7 heptoxides were investigated by computational methods as both isolated molecules and in the solid-state. The metal–oxygen–metal bending angle of the single molecule increased with increasing atomic number, with Re2O7 preferring a linear structure. Natural bond orbital and localized orbital bonding analyses indicate that there is a three-center covalent bond between the metal atoms and the bridging oxygen, and the increasing ionic character of the bonds favors larger bond angles. The calculations accurately reproduce the experimental crystal structures within a few percent. Analysis of the band structures and density of states shows similar bonding for all of the solid-state heptoxides, including the presence of the three-center covalent bond. DFT+U simulations show that PBE-D3 underpredicts the band gap by ∼0.2 eV due to an undercorrelation of the metal d conducting states. Homologue and compression studies show that Re2O7 adopts a polymeric structure... |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|