Surface Energies of LaMnO3 High-Index Surfaces Obtained from Density-Functional Theory

• Published in: Journal of physical chemistry. C 2023-05, Vol.127 (20), p.9814-9822
• Main Authors: Mantz, Yves A., Lee, Yueh-Lin
• Format: Article
• Language: English
• Subjects: C: Physical Properties of Materials and Interfaces; chemical structure; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; layers; phase transitions; surface energy; thickness
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.3c00984

The first six cubic LaMnO3 high-index surfaces, (210), (211), (221), (310), (311), and (320), are examined for the first time. The unrelaxed and relaxed surface energies of the surfaces are computed as a function of surface model thickness using unrelaxed and relaxed surface models, respectively. The (210), (320), (211), and (221) surfaces are found to be more stable than the low-index (011) and (111) surfaces. Helping to explain this result, the surface terminations of the (210), (320), (211), or (221) surface are seen to exhibit a rotational relaxation of the MnO6 or oxygen octahedra extending from the surface into the bulk. By contrast, the relaxed surface energies of the (310) and (311) surfaces are concluded to be difficult to determine due to a structural transformation or phase change in the surface models of the surfaces away from cubic LaMnO3. The finding of a phase change is important. It indicates that a phase change in the surface models of a surface for another material could occur if the surface is relatively open and a different phase of the material is stable at low temperature. When modeling such a surface, two steps are suggested to be taken.