Rationalizing accurate structure prediction in the meta-GGA SCAN functional

Abstract

Author(s): Yang, JH; Kitchaev, DA; Ceder, G | Abstract: The ability of first-principles computational methods to reproduce ground-state crystal structure selection is key to their application in the discovery of new materials, and yet presents a formidable challenge due to the low-energy scale of the problem and lack of systematic error cancellation. The recently developed Strongly Constrained and Appropriately Normed (SCAN) functional is notable for accurately calculating physical properties such as formation energies and in particular, correctly predicting ground-state structures. Here, we attempt to rationalize the improved structure prediction accuracy in SCAN by investigating the relationship between preferred coordination environments, the description of attractive van der Waals (vdW) interactions, and the overall ground-state prediction in bulk main-group solids. We observe a systematic undercoordination error in the traditional Perdew, Burke, and Ernzerhof (PBE) functional which is not present in SCAN results and find that semiempirical dispersion corrections in the form of PBE+D3 fail to correct this error in a consistent or physical manner. We conclude that the medium-range vdW interaction is correctly parametrized in SCAN and yields meaningful relative energies between coordination environments.