A cross-entropy corrected hybrid multiconfiguration pair-density functional theory for complex molecular systems
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) th...
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Nature Portfolio
2025-01-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-55524-z |
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| author | Rulin Feng Igor Ying Zhang Xin Xu |
| author_facet | Rulin Feng Igor Ying Zhang Xin Xu |
| author_sort | Rulin Feng |
| collection | DOAJ |
| description | 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. |
| format | Article |
| id | doaj-art-19af9bf58fbd4039818e53adc8d7dbfa |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-19af9bf58fbd4039818e53adc8d7dbfa2025-01-05T12:41:13ZengNature PortfolioNature Communications2041-17232025-01-0116111410.1038/s41467-024-55524-zA cross-entropy corrected hybrid multiconfiguration pair-density functional theory for complex molecular systemsRulin Feng0Igor Ying Zhang1Xin Xu2Shanghai 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 UniversityShanghai 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 UniversityShanghai 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 UniversityAbstract 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.https://doi.org/10.1038/s41467-024-55524-z |
| spellingShingle | Rulin Feng Igor Ying Zhang Xin Xu A cross-entropy corrected hybrid multiconfiguration pair-density functional theory for complex molecular systems Nature Communications |
| title | A cross-entropy corrected hybrid multiconfiguration pair-density functional theory for complex molecular systems |
| title_full | A cross-entropy corrected hybrid multiconfiguration pair-density functional theory for complex molecular systems |
| title_fullStr | A cross-entropy corrected hybrid multiconfiguration pair-density functional theory for complex molecular systems |
| title_full_unstemmed | A cross-entropy corrected hybrid multiconfiguration pair-density functional theory for complex molecular systems |
| title_short | A cross-entropy corrected hybrid multiconfiguration pair-density functional theory for complex molecular systems |
| title_sort | cross entropy corrected hybrid multiconfiguration pair density functional theory for complex molecular systems |
| url | https://doi.org/10.1038/s41467-024-55524-z |
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