State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
J Chem Phys. 2012 May 7;136(17):174103. doi: 10.1063/1.3703893.
Following the XYG3 model which uses orbitals and density from B3LYP, an empirical doubly hybrid (DH) functional is developed by using inputs from PBE0. This new functional, named xDH-PBE0, has been tested on a number of different molecular properties, including atomization energies, bond dissociation enthalpies, reaction barrier heights, and nonbonded interactions. From the results obtained, xDH-PBE0 not only displays a significant improvement with respect to the parent PBE0, but also shows a performance that is comparable to XYG3. Arguably, while PBE0 is a parameter-free global hybrid (GH) functional, the B3LYP GH functional contains eight fit parameters. From a more general point of view, the present work points out that reliable and general-purpose DHs can be obtained with a limited number of fit parameters.
沿用采用 B3LYP 轨道和密度的 XYG3 模型，我们利用 PBE0 的输入开发了一个经验双杂化（DH）泛函。这个新的泛函名为 xDH-PBE0，已经在许多不同的分子性质上进行了测试，包括原子化能、键离解焓、反应势垒高度和非键相互作用。从得到的结果来看，xDH-PBE0 不仅相对于原始的 PBE0 有显著的改进，而且性能与 XYG3 相当。可以说，虽然 PBE0 是一个无参数的全局杂化（GH）泛函，但 B3LYP GH 泛函包含八个拟合参数。从更一般的角度来看，本工作指出，通过使用有限数量的拟合参数，可以获得可靠且通用的 DH。
