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08:45
Fabrication of Spatially Confined Complex Oxides
Published on: July 1, 2013
Covalent bonding in heavy metal oxides
Paul S Bagus1, Connie J Nelin2, Dave A Hrovat1
1Department of Chemistry and the Center for Advanced Scientific Computing and Modeling, University of North Texas, Denton, Texas 76203-5017, USA.
The Journal of Chemical Physics
|April 10, 2017
Summary
This study reveals that both f and d orbital interactions significantly contribute to covalent bonding in lanthanide and actinide oxides. The importance of f-orbital covalency diminishes relative to d-orbital covalency as electron occupation increases.
Area of Science:
- Materials Science
- Quantum Chemistry
- Inorganic Chemistry
Background:
- Covalent bonding in lanthanide and actinide oxides is crucial for their properties.
- Previous analyses often overlooked the role of d orbitals in metal-oxygen interactions.
Purpose of the Study:
- To quantify the contributions of 4f/5f-O2p and 5d/6d-O2p interactions to covalent bonding.
- To investigate the relative importance of f and d orbital covalency.
- To identify trends and driving factors in these interactions.
Main Methods:
- Novel theoretical methods were employed.
- Quantification of energetic contributions of specific orbital interactions.
- Analysis of trends based on oxidation state and electron occupation.
Main Results:
- Both f and d orbital covalencies are of comparable importance in bonding.
- Covalent mixing increases with higher nominal oxidation states.
- The relative importance of nf covalency decreases compared to (n+1)d covalency as nf occupation increases.
Conclusions:
- f and d orbital interactions are key to understanding covalent bonding in these oxides.
- Oxidation state and electron occupation significantly influence bonding characteristics.
- Atomic properties of metal cations dictate these bonding trends.
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