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<p>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 Cr<sub>2</sub> 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.</p>

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

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年1月2日

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  • Rulin Feng,
  • Igor Ying Zhang,
  • Xin Xu

摘要

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.