Surface terminations of hematite (α-Fe2O3) exposed to oxygen, hydrogen, or water: dependence on the density functional theory methodology.

Hematite (α-Fe2O3) is the most stable and abundant iron oxide in nature, and is used in many important environmental and industrial technologies, such as waste-water treatment, gas sensors, and photoelectrocatalysis. A clear understanding of the structure, composition, and chemistry of the hematite surface is crucial for improving its function in these technologies. Here we employ density functional theory (DFT) together with the DFT+U approach using semi-local functionals, as well as hybrid functionals, to study the structure, stability, and electronic properties of the (0 0 0 1) surface exposed to oxygen, hydrogen, or water. The use of hybrid functionals allow for a description of strong correlation without the need for atom-specific empirical parameters (i.e. U). However, we find that PBE+U, and in part also PBE, give similar results as the hybrid functional HSE(12%) in terms of structure optimization. When it comes to stability, work function, as well as electronic structure, the results are sensitive to the choice of functionals, but we cannot judge which level of functional is most appropriate due to the lack of experimental observations.

Variation in seed fatty acid composition and sequence divergence in the FAD2 gene coding region between wild and cultivated sesame.

Sesame germplasm harbors genetic diversity which can be useful for sesame improvement in breeding programs. Seven accessions with different levels of oleic acid were selected from the entire USDA sesame germplasm collection (1232 accessions) and planted for morphological observation and re-examination of fatty acid composition. The coding region of the FAD2 gene for fatty acid desaturase (FAD) in these accessions was also sequenced. Cultivated sesame accessions flowered and matured earlier than the wild species. The cultivated sesame seeds contained a significantly higher percentage of oleic acid (40.4%) than the seeds of the wild species (26.1%). Nucleotide polymorphisms were identified in the FAD2 gene coding region between wild and cultivated species. Some nucleotide polymorphisms led to amino acid changes, one of which was located in the enzyme active site and may contribute to the altered fatty acid composition. Based on the morphology observation, chemical analysis, and sequence analysis, it was determined that two accessions were misnamed and need to be reclassified. The results obtained from this study are useful for sesame improvement in molecular breeding programs.