Strongly constrained and appropriately normed density functional theory exchange-correlation functional applied to rare earth oxides

Density functional theory (DFT) is one of the main tools for studying the electronic structure of solids and molecules. Nevertheless, one of the main drawbacks of the implementation of DFT is the so-called self-interaction error (SIE) that can yield undesired delocalization errors and ultimately results in the prediction of metals instead of experimentally observed insulators. These SIEs can be amended by using more evolved exchange-correlation functionals than standard local density approximation such as the recent meta-generalized gradient approximation strongly constrained and appropriately normalized (SCAN) functional that is successful in describing electronic properties of 3d transition metal oxides. Nevertheless, the ability of such a functional to describe electronic properties of materials involving more localized states such as 4 f orbitals is rather elusive. Here, we show that, even though SCAN can sometimes predict the insulating character of some compounds, it often fails in predicting the correct band edge orbital character of insulators. By comparing our SCAN results with benchmark simulations obtained with more accurate hybrid DFT calculations, we ascribe this failure to insufficiently amended SIEs by SCAN that results in an underestimation of Hund's splitting associated with 4 f states. Thus, although appropriate for 3d transition metal elements, the SCAN functional is not yet a sufficient platform for studying electronic properties of materials involving rare-earth elements where 4 f states play a key role in the properties.

Automated summary

Density functional theory (DFT) is a main tool for studying the electronic structure, but suffers from the self-interaction error (SIE) which causes delocalization errors and metal predictions instead of insulators. The recently developed SCAN functional is successful for 3d transition metal oxides, but fails in describing materials involving more localized states like 4 f orbitals. Insufficiently amended SIEs in SCAN result in an underestimation of Hund's splitting for 4 f states. Therefore, SCAN is not sufficient for studying electronic properties of materials involving rare-earth elements.