A cross-entropy corrected hybrid multiconfiguration pair-density functional theory for complex molecular systems

Rulin Feng, Igor Ying Zhang () and Xin Xu ()
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Rulin Feng: Fudan University
Igor Ying Zhang: Fudan University
Xin Xu: Fudan University

Nature Communications, 2025, vol. 16, issue 1, 1-14

Abstract: Abstract Hybrid density functionals, such as B3LYP and PBE0, have achieved remarkable success by substantially improving over their parent methods, namely Hartree-Fock and the generalized gradient approximation, and generally outperforming the second-order Møller-Plesset perturbation theory (MP2) that is more expensive. Here, we extend the linear scheme of hybrid multiconfiguration pair-density functional theory (HMC-PDFT) by incorporating a cross-entropy ingredient to balance the description of static and dynamic correlation effects, leading to a consistent improvement on both exchange and correlation energies. The B3LYP-like translated on-top functional (tB4LYP) developed along this line not only surpasses the accuracy of its parent methods, the complete active space self-consistent field (CASSCF) and the original MC-PDFT functionals (tBLYP and tB3LYP), but also outperforms the widely used complete active space second-order perturbation theory (CASPT2). Remarkably, while remaining satisfactory for general purpose, tB4LYP shows superior accuracy for challenging cases like the Cr2 dissociation and the associated low-lying vibrational energies, the ethylene torsional rotation and the ethyne diabatic colinear dissociations, with the significantly lower computational cost than CASPT2.

Date: 2025
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DOI: 10.1038/s41467-024-55524-z

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