Structure and Bonding in a Diamond‐Shaped Tin Cluster Possessing a cyclo ‐Sn 4 Core
- Award ID(s):
- 1954808
- PAR ID:
- 10293652
- Date Published:
- Journal Name:
- Chemistry – A European Journal
- Volume:
- 26
- Issue:
- 28
- ISSN:
- 0947-6539
- Page Range / eLocation ID:
- 6126 to 6129
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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ABSTRACT We investigate the local atomic and electronic structure, thermodynamic stability, and defect chemistry ofA6B2O17(A= Zr/Hf,B= Nb/Ta) oxides using first‐principles density functional theory (DFT) calculations. We examine both ordered unit cells as well as fully disordered special quasirandom structures to clearly discern the effects of cation disorder. Structural predictions align closely with previous experimental results and follow established ionic radii trends. The electronic structure is strongly dependent onB‐cation species:A6Ta2O17compositions have ~30% larger band gaps than theirA6Nb2O17counterparts. Defect chemistry is similar for all compositions, with anion vacancies being more energetically favorable than corresponding cation defects. All exploredA6B2O17compositions are enthalpically unstable with respect to theirAO2andB2O5competing oxides and are therefore classified as entropy‐stabilized materials, supporting prior experimental results. The pronounced agreement between our disordered supercell predictions and experimental measurements indicates all exploredA6B2O17compositions contain substantial cation disorder across all 6‐, 7‐, and 8‐coordinated sites. Our findings collectively provide a fundamental understanding of theA6B2O17material family through DFT calculations, establishing a framework for future compositional tuning to engineer targeted material properties.more » « less
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