Improved description of hematite surfaces by the SCAN functional

摘要

Controversies on the surface termination of alpha-Fe2O3 (0001) focus on its surface stoichiometry dependence on the oxygen chemical potential. Density functional theory (DFT) calculations applying the commonly accepted Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional to a strongly correlated system predict the best matching surface termination, but would produce a delocalization error, resulting in an inappropriate bandgap, and thus are not applicable for comprehensive hematite system studies. Besides, the widely applied PBE+U scheme cannot provide evidence for existence of some of the successfully synthesized stoichiometric alpha-Fe2O3 (0001) surfaces. Hence, a better scheme is needed for hematite DFT studies. This work investigates whether the strongly constrained and appropriately normed (SCAN) approximation reported by Perdew et al. could provide an improved result for the as-mentioned problem, and whether SCAN can be applied to hematite systems. By comparing the results calculated with the PBE, SCAN, PBE+U, and SCAN+U schemes, we find that SCAN and SCAN+U improves the description of the electronic structure of different stoichiometric alpha-Fe2O3 (0001) surfaces with respect to the PBE results, and that they give a consistent prediction of the surface terminations. Besides, the bulk lattice constants and the bulk density of states are also improved with the SCAN functional. This study provides a general characterization of the alpha-Fe2O3 (0001) surfaces and rationalizes how the SCAN approximation improves the results of hematite surface calculations.