Toward Efficient and Unified Treatment of Static and Dynamic Correlations in Generalized Kohn-Sham Density Functional Theory

Yizhen Wang; Zihan Lin; Runhai Ouyang; Bin Jiang; Igor Ying Zhang; Xin Xu

doi:10.1021/jacsau.4c00488

Toward Efficient and Unified Treatment of Static and Dynamic Correlations in Generalized Kohn-Sham Density Functional Theory

JACS Au. 2024 Aug 12;4(8):3205-3216. doi: 10.1021/jacsau.4c00488. eCollection 2024 Aug 26.

Authors

Yizhen Wang¹, Zihan Lin¹, Runhai Ouyang², Bin Jiang^{3

4}, Igor Ying Zhang^{1

4

5}, Xin Xu^{1

4}

Affiliations

¹ Shanghai Key Laboratory of Molecular Catalysis and Innovation Materials, Collaborative Innovation Centre of Chemistry for Energy Materials, MOE Laboratory for Computational Physical Science, Department of Chemistry, Fudan University, Shanghai 200438, China.
² Materials Genome Institute, Shanghai University, Shanghai 200444, China.
³ Key Laboratory of Precision and Intelligent Chemistry, Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230026, China.
⁴ Hefei National Laboratory, Hefei 230088, China.
⁵ Shanghai Key Laboratory of Bioactive Small Molecules, Shanghai200032, China.

Abstract

Accurate description of the static correlation poses a persistent challenge in electronic structure theory, particularly when it has to be concurrently considered with the dynamic correlation. We develop here a method in the generalized Kohn-Sham density functional theory (DFT) framework, named R-xDH7-SCC15, which achieves an unprecedented accuracy in capturing the static correlation, while maintaining a good description of the dynamic correlation on par with the state-of-the-art DFT and wave function theory methods, all grounded in the same single-reference black-box methodology. Central to R-xDH7-SCC15 is a general-purpose static correlation correction (SCC) model applied to the renormalized XYG3-type doubly hybrid method (R-xDH7). The SCC model development involves a hybrid machine learning strategy that integrates symbolic regression with nonlinear parameter optimization, aiming to achieve a balance between generalization capability, numerical accuracy, and interpretability. Extensive benchmark studies confirm the robustness and broad applicability of R-xDH7-SCC15 across a diverse array of main-group chemical scenarios. Notably, it displays exceptional aptitude in accurately characterizing intricate reaction kinetics and dynamic processes in regions distant from equilibrium, where the influence of static correlation is most profound. Its capability to consistently and efficiently predict the whole energy profiles, activation barriers, and reaction pathways within a user-friendly "black-box" framework represents an important advance in the field of electronic structure theory.