English

Reducing Self-Interaction Error in Transition-Metal Oxides with Different Exact-Exchange Fractions for Energy and Density

Materials Science 2026-04-13 v4 Strongly Correlated Electrons Chemical Physics Computational Physics

Abstract

Density functional theory (DFT) in chemistry and materials science aims for "chemical accuracy," but this goal is challenged by the need to approximate the exact exchange-correlation (XC) energy functional. The r2^2SCAN, meta-generalized gradient approximation to the XC functional fulfills 17 exact constraints of the XC energy, and has significantly boosted prediction accuracy for molecules and materials. However, r2^2SCAN remains inadequate at predicting properties of open \textit{d} and \textit{f} transition-metal strongly correlated compounds, such as band gaps, magnetic moments, and oxidation energies. Prediction inaccuracies of r2^2SCAN energies arise from functional and density-driven errors, mainly resulting from the DFT self-interaction error. We propose the r2^2SCANY@r2^2SCANX method to mitigate the self-interaction error of XC functionals for the accurate simulations of electronic, magnetic, and thermochemical properties of transition metal oxides. r2^2SCANY@r2^2SCANX uses different fractions of exact Hartree-Fock exchange: X for the electronic density and Y for the density functional approximation of the total energy, thereby simultaneously addressing functional-driven and density-driven inaccuracies. Building just on 1 (or maximum 2) parameters that apply unchanged to \emph{s-p}-bonded systems, we demonstrate that, r2^2SCANY@r2^2SCANX improves upon the r2^2SCAN predictions for 20 highly correlated oxides and even outperforms the highly parameterized DFT(r2^2SCAN)+\emph{U} method -- the state-of-the-art approach to predict strongly correlated materials. Prediction uncertainties for oxidation energies and magnetic moments of transition metal oxides are significantly reduced by r2^2SCAN10@r2^2SCAN50 and band gaps with r2^2SCAN10@r2^2SCAN. r2^2SCAN10@r2^2SCAN50 diminishes the density-driven error of the energy in r2^2SCAN and r2^2SCAN10.

Cite

@article{arxiv.2506.20635,
  title  = {Reducing Self-Interaction Error in Transition-Metal Oxides with Different Exact-Exchange Fractions for Energy and Density},
  author = {Harshan Reddy Gopidi and Ruiqi Zhang and Yanyong Wang and Abhirup Patra and Jianwei Sun and Adrienn Ruzsinszky and John P. Perdew and Pieremanuele Canepa},
  journal= {arXiv preprint arXiv:2506.20635},
  year   = {2026}
}