Doubly Hybrid Functionals Close to Chemical Accuracy for Both Finite and Extended Systems: Implementation and Test of XYG3 and XYGJ-OS

While being widely used to understand the chemical reactions in heterogeneous catalysis or other multi-disciplinary systems, a great challenge that semilocal and hybrid density functional approximations (DFAs) are facing is to deliver a uniformly accurate description for both finite and extended systems. Herein, we perform reliable and well-converged periodic calculations of two doubly hybrid approximations (DHAs), XYG3 and XYGJ-OS, and demonstrate that the good accuracy of DHAs achieved for molecules is transferable to the semiconductors and insulators. Such an accuracy is not only for energetic properties but also for the first- and second-order response properties, which is general for different kinds of chemical environments, including simple cubic bulks, perovskite-type transition metal oxides like TiO2, and heterogeneous systems like CO adsorption on the NaCl(100) surface. The present finding has strengthened the predictive power of DFT, which not only will inspire the future development of the top-rung DFAs but also will boost their applications in multidisciplinary studies with high accuracy and efficiency.

Automated summary

The study demonstrates that the accuracy of doubly hybrid approximations for molecules can be transferred to semiconductors and insulators, and is applicable to different chemical environments with good performance in first- and second-order response properties. This finding strengthens the predictive power of DFT and will inspire future development of density functional approximations with high accuracy and efficiency.