Su Neil Qiang, Xu Xin
Collaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, MOE Laboratory for Computational Physical Science, Department of Chemistry, Fudan University, Shanghai 200433, China.
J Chem Phys. 2014 May 14;140(18):18A512. doi: 10.1063/1.4866457.
In this work, the adiabatic connection (AC) formalism, coordinate scaling relations, and the second order Görling-Levy perturbation theory (GL2) are first reviewed. Emphasis is laid upon the construction of the AC integrand (Wxc(λ)), with suitable input data {Wxc(0), Wxc'(0), Wxc(1) and the proper asymptotic behavior on λ(-1/2) as λ → ∞. This leads to a non-empirical DH functional, namely, PBE-ACDH. The PBE-ACDH functional is unique in that it explicitly considers contributions from density scaling and singles, and it utilizes density and orbital information from the PBE functional, which has a local multiplicative potential, being most compatible with the GL2 theory. Systematical tests on heats of formation, bond dissociation enthalpies, reaction barrier heights, and nonbonded interactions, using some well-established benchmarking sets, suggest that PBE-ACDH is a significant improvement over its parent functional PBE, as well as PBE0, Becke's Half-and-Half (PBE-HH), and GL2. The physical insight gained in the present work should prove useful for the further development of new functionals.
在这项工作中，首先回顾了绝热连接（AC）形式、坐标缩放关系和二阶戈林-利维微扰理论（GL2）。重点在于构建AC被积函数（Wxc(λ)），并给出合适的输入数据{Wxc(0)、Wxc'(0)、Wxc(1)}以及λ→∞时λ^(-1/2)的正确渐近行为。这导致了一种非经验的双杂化泛函，即PBE - ACDH。PBE - ACDH泛函的独特之处在于它明确考虑了密度缩放和单重态的贡献，并且利用了来自PBE泛函的密度和轨道信息，PBE泛函具有局部乘性势，与GL2理论最为兼容。使用一些成熟的基准集对生成热、键解离焓、反应势垒高度和非键相互作用进行的系统测试表明，PBE - ACDH相对于其母泛函PBE以及PBE0、贝克半混合泛函（PBE - HH）和GL2有显著改进。在本工作中获得的物理见解应证明对新泛函的进一步发展有用。
