Improving XYG3-type doubly hybrid approximation using self-interaction corrected SCAN density and orbitals via the PZ-SIC framework: The xDH@SCAN(SIC) approach.
Improving XYG3-type doubly hybrid approximation using self-interaction corrected SCAN density and orbitals via the PZ-SIC framework: The xDH@SCAN(SIC) approach.
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DOI：
10.1063/5.0174040
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发表时间：
2023-12
期刊：
影响因子：
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通讯作者：
Sheng Bi;Shirong Wang;Igor Ying Zhang;Xin Xu
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文献类型：
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作者：
Sheng Bi;Shirong Wang;Igor Ying Zhang;Xin Xu
XYG 3型双杂交（xDH）近似在描述各种化学和物理相互作用方面的准确性得到了广泛的认可。然而，最近的一项研究[Song等人，《物理化学杂志》12，800-807（2021）]已经强调了xDH方法在计算NaCl分子解离中的局限性。这个问题已经涉及到的密度和轨道用于评估的能量在xDH方法，这是从较低的梯级混合密度泛函近似（DFA）和显示大量的密度误差的解离极限。在这项工作中，我们系统地研究了密度对几个具有挑战性的数据集的影响，并发现与半局部和混合DFA相比，xDH方法对密度误差不那么敏感。此外，我们证明了自相互作用校正的SCAN密度的方法提供了上级的准确性相比，自洽的SCAN密度和Hartree-Fock密度的方法，证明了进行电荷分析的异源二聚体，如NaCl和LiF的解离。基于这些见解，我们提出了一个五参数xDH方法，使用PZ-SIC方案校正的SCAN密度和轨道。这种新的xDH@SCAN（SIC）方法在各种具有挑战性的系统中提供了平衡和准确的描述。
XYG3-type doubly hybrid (xDH) approximations have gained widespread recognition for their accuracy in describing a diverse range of chemical and physical interactions. However, a recent study [Song et al., J. Phys. Chem. Lett. 12, 800-807 (2021)] has highlighted the limitation of xDH methods in calculating the dissociation of NaCl molecules. This issue has been related to the density and orbitals used for evaluating the energy in xDH methods, which are obtained from lower-rung hybrid density functional approximations (DFAs) and display substantial density errors in the dissociation limit. In this work, we systematically investigate the influence of density on several challenging datasets and find that xDH methods are less sensitive to density errors compared to semi-local and hybrid DFAs. Furthermore, we demonstrate that the self-interaction corrected SCAN density approach offers superior accuracy compared to the self-consistent SCAN density and Hartree-Fock density approaches, as evidenced by performing charge analysis on the dissociation of heterodimers, such as NaCl and LiF. Building on these insights, we propose a five-parameter xDH method using the SCAN density and orbitals corrected by the PZ-SIC scheme. This new xDH@SCAN(SIC) method provides a balanced and accurate description across a wide range of challenging systems.