Cerium Oxides without $U$: The Role of Many-Electron Correlation

Abstract

Electron transfer with changing occupation in the 4f subshell poses a considerable challenge for quantitative predictions in quantum chemistry. Using the example of cerium oxide, we identify the main deficiencies of common parameter-dependent one-electron approaches, such as density functional theory (DFT) with a Hubbard correction, or hybrid functionals. As a response, we present the first benchmark of ab initio many-electron theory for electron transfer energies and lattice parameters under periodic boundary conditions. We show that the direct random phase approximation clearly outperforms all DFT variations. From this foundation, we, then, systematically improve even further. Periodic second-order Møller-Plesset perturbation theory meanwhile manages to recover standard hybrid functional values. Using these approaches to eliminate parameter bias allows for highly accurate benchmarks of strongly correlated materials, the reliable assessment of various density functionals, and functional fitting via machine-learning.

arXiv comment7 pages, 3 figures, 1 table

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• Approaching the basis-set limit of the dRPA correlation energy with explicitly correlated and Projector Augmented-wave methods
• Ground-States for Metals from Converged Coupled Cluster Calculations
• Optimizing Hubbard U parameters for Enhanced Description of Electronic and Magnetic Properties in CrI${}_3$ Monolayers and Bilayers
• Coupled cluster theory for the ground and excited states of two dimensional quantum dots