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 Phys Chem A. 2015 Mar 5;119(9):1590-9. doi: 10.1021/jp507711t. Epub 2014 Oct 21.
We have systematically analyzed the error accumulations in the adhesive energies for a series of hydrogen molecular chains calculated by various kinds of density functional theory (DFT) methods. In particular, we have focused on some representative doubly hybrid (DH) functionals of either the B2PLYP type (B2PLYP, B2PLYP-D, and B2GP-PLYP) or the XYG3 type (XYG3, XYGJ-OS, and xDH-PBE0). The hydrogen molecular chain models have recently been proposed by Zheng et al. (J. Chem. Phys. 2012, 137, 214106) to identify the delocalization errors (DEs) in thermodynamic properties. From the perspective of DEs, it is shown here that the XYG3 type of DH functionals yield good performance on the calculated adhesive energies due to the minimizing effects of DEs, highlighting the underlying physics for the successes or failures of the approximate functionals. Examination was also extended to HF-DFT, where DFT energies are evaluated with the Hartree-Fock (HF) densities.
我们系统地分析了通过各种密度泛函理论（DFT）方法计算的一系列氢分子链的结合能中的误差累积。特别地，我们关注了一些具有代表性的双杂化（DH）泛函，包括B2PLYP类型（B2PLYP、B2PLYP-D和B2GP-PLYP）或XYG3类型（XYG3、XYGJ-OS和xDH-PBE0）。氢分子链模型最近由郑等人（《化学物理杂志》，2012年，137卷，214106页）提出，用于识别热力学性质中的离域误差（DEs）。从DEs的角度来看，这里表明XYG3类型的DH泛函由于DEs的最小化效应，在计算结合能方面表现良好，突出了近似泛函成功或失败的潜在物理原理。研究还扩展到了HF-DFT，其中DFT能量是用Hartree-Fock（HF）密度来评估的。
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