Laboratoire de Chimie Théorique, Université Pierre et Marie Curie and CNRS, 75005 Paris, France.
J Chem Phys. 2011 Feb 14;134(6):064113. doi: 10.1063/1.3544215.
We provide a rigorous derivation of a class of double-hybrid approximations, combining Hartree-Fock exchange and second-order Møller-Plesset correlation with a semilocal exchange-correlation density functional. These double-hybrid approximations contain only one empirical parameter and use a density-scaled correlation energy functional. Neglecting density scaling leads to a one-parameter version of the standard double-hybrid approximations. We assess the performance of these double-hybrid schemes on representative test sets of atomization energies and reaction barrier heights, and we compare to other hybrid approximations, including range-separated hybrids. Our best one-parameter double-hybrid approximation, called 1DH-BLYP, roughly reproduces the two parameters of the standard B2-PLYP or B2GP-PLYP double-hybrid approximations, which shows that these methods are not only empirically close to an optimum for general chemical applications but are also theoretically supported.
我们提供了一类双杂交近似的严格推导，将 Hartree-Fock 交换和二阶 Møller-Plesset 相关与半局部交换相关密度泛函相结合。这些双杂交近似只包含一个经验参数，并使用密度标度相关能量泛函。忽略密度标度会导致标准双杂交近似的一个参数版本。我们在代表性的原子化能和反应势垒高度测试集上评估这些双杂交方案的性能，并与其他混合近似方法进行比较，包括区间分离混合方法。我们最好的单参数双杂交近似，称为 1DH-BLYP，大致再现了标准 B2-PLYP 或 B2GP-PLYP 双杂交近似的两个参数，这表明这些方法不仅在经验上接近一般化学应用的最佳选择，而且在理论上也得到了支持。
