Feng Rulin, Zhang Igor Ying, Xu Xin
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, China.
Shanghai Key Laboratory of Bioactive Small Molecules, Shanghai, China.
Nat Commun. 2025 Jan 2;16(1):235. doi: 10.1038/s41467-024-55524-z.
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 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.
杂化密度泛函，如B3LYP和PBE0，通过在其母体方法（即哈特里 - 福克方法和广义梯度近似）的基础上有实质性改进，取得了显著成功，并且总体上优于计算成本更高的二阶莫勒 - 普莱塞特微扰理论（MP2）。在此，我们通过纳入交叉熵成分来平衡静态和动态相关效应的描述，扩展了杂化多组态对密度泛函理论（HMC - PDFT）的线性方案，从而在交换能和相关能方面都实现了持续改进。沿着这条路线发展的类B3LYP的顶位翻译泛函（tB4LYP）不仅超越了其母体方法——完全活性空间自洽场（CASSCF）和原始的MC - PDFT泛函（tBLYP和tB3LYP）的精度，而且还优于广泛使用的完全活性空间二阶微扰理论（CASPT2）。值得注意的是，tB4LYP在满足通用要求的同时，对于诸如Cr解离及其相关的低振动能、乙烯扭转旋转和乙炔绝热共线解离等具有挑战性的情况显示出卓越的精度，且计算成本比CASPT2显著更低。
