- Title
- Electronic structure and high-temperature thermochemistry of oxygen-deficient BaMO3 (M = Ti - Cu) perovskites
- Creator
- Ghose, Krishna K.; Bayon, Alicia; Page, Alister J.
- Relation
- ARC.LE170100032 http://purl.org/au-research/grants/arc/LE170100032
- Relation
- The Journal of Physical Chemistry Part C Vol. 124, Issue 49, p. 27055-27063
- Publisher Link
- http://dx.doi.org/10.1021/acs.jpcc.0c06369
- Publisher
- American Chemical Society
- Resource Type
- journal article
- Date
- 2020
- Description
- Alkaline-earth perovskites are of particular interest for high-temperature energy conversion processes because of their mixed-valence charge states, which significantly affect their chemical and thermal stability. However, in many cases, the thermochemical properties and stabilities of such perovskites under high-temperature conditions remain uncharacterized. We present here a systematic study of the stability, electronic structures, and thermochemical properties of oxygen-deficient BaMO3 (M = Ti – Cu) perovskites using accurate first-principles calculations. The electronic structure across this series of perovskites varies from a semiconductor/insulator to a ferromagnetic and ultimately metallic character, and this leads to a change in the intrinsic stability of the perovskite lattices of more than 700 kJ mol–1. However, these intrinsic trends are disrupted significantly when explicit thermochemical corrections, relevant to high-temperature applications, are included in reduction free energies. The key factor in this respect is the temperature-dependent entropic contribution, which is distinct for each perovskite. We demonstrate that this is a reflection of the unique instabilities of each perovskite structure at high temperatures.
- Subject
- alkaline-earth perosvkites; thermochemical properties; high temperature; temperature-dependent; SDG 7
- Identifier
- http://hdl.handle.net/1959.13/1471360
- Identifier
- uon:48659
- Identifier
- ISSN:1932-7447
- Language
- eng
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