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Computational workflows for perovskites: case study for lanthanide manganites

Kraus, Peter; Raiteri, Paolo; Gale, Julian D.

Robust computational workflows are important for explorative computational studies, especially for cases where detailed knowledge of the system structure or other properties is not available. In this work, we propose a computational protocol for appropriate method selection for the study of lattice constants of perovskites using density functional theory, based strictly on open source software. The protocol does not require a starting crystal structure. We validate this protocol using a set of crystal structures of lanthanide manganites, surprisingly finding N12+U to be the best performing method for this class of materials out of the 15 density functional approximations studied. We also highlight that +U values derived from linear response theory are robust and their use leads to improved results. We investigate whether the performance of methods for predicting the bond length of related gas phase diatomics correlates with their performance for bulk structures, showing that care is required when interpreting benchmark results. Finally, using defective LaMnO3 as a case study, we investigate whether the four shortlisted methods (HCTH120, OLYP, N12+U, PBE+U) can computationally reproduce the experimentally determined fraction of MnIV+ at which the orthorhombic to rhombohedral phase transition occurs. The results are mixed, with HCTH120 providing good quantitative agreement with experiment, but failing to capture the spatial distribution of defects linked to the electronic structure of the system.
Published in: Physical Chemistry Chemical Physics, 10.1039/d3cp00041a, Royal Society of Chemistry