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Published on: October 27, 2018
Formation and characterization of two FeO3 isomers in solid argon
1Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Advanced Materials Laboratory, Fudan University, Shanghai 200433, P. R. China.
The Journal of Physical Chemistry. A
|October 3, 2008
Summary
Researchers synthesized two iron trioxide (Fe2O3) isomers. One isomer, a complex with dioxygen, rearranges to a more stable iron trioxide structure upon visible light irradiation.
Area of Science:
- Inorganic Chemistry
- Spectroscopy
- Computational Chemistry
Background:
- Iron oxides are crucial compounds with diverse applications.
- Understanding the structure and reactivity of iron oxides is essential for materials science.
- Previous studies have explored various iron oxide species, but the characterization of specific isomers remains an active area of research.
Purpose of the Study:
- To prepare and characterize two isomers of iron trioxide (Fe2O3).
- To investigate the formation and structural properties of an intermediate iron monoxide-dioxygen complex.
- To determine the conditions for isomer interconversion and the properties of the more stable iron trioxide isomer.
Main Methods:
- Matrix isolation infrared spectroscopy was employed for experimental characterization.
- Theoretical calculations were used to predict molecular structures and electronic states.
- Laser evaporation of iron oxide targets generated the initial molecules.
- Annealing in solid argon facilitated the formation of the iron monoxide-dioxygen complex.
- Visible light irradiation was used to induce isomer rearrangement.
Main Results:
- Two isomers of iron trioxide (Fe2O3) were successfully prepared and characterized.
- A transient iron monoxide-dioxygen complex, (eta(2)-O2)FeO, was formed spontaneously.
- This complex was predicted to have a planar C2v structure with a 5B2 ground state.
- Visible light irradiation (λ > 500 nm) induced the rearrangement of the (eta(2)-O2)FeO complex to a more stable iron trioxide isomer.
- The stable iron trioxide isomer was predicted to possess a planar D3h symmetry and a closed-shell singlet ground state, with iron in a +6 oxidation state.
Conclusions:
- The study successfully characterized two Fe2O3 isomers, providing insights into their formation and stability.
- The findings demonstrate the photoinduced interconversion between different iron trioxide structures.
- The identification of a high-valent iron (+6) in the stable isomer opens avenues for exploring novel iron chemistry.
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