用于模拟金属原子交联聚乙烯链的 DFT 泛函。DLPNO–CCSD(T) 基准计算,The Journal of Physical Chemistry A

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用于模拟金属原子交联聚乙烯链的 DFT 泛函。DLPNO–CCSD(T) 基准计算
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2021-08-24 , DOI: 10.1021/acs.jpca.1c04793
Martin Blaško ₁ , Lukáš F Pašteka ₂ , Miroslav Urban ₂

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用于计算由选定金属原子 (M) 交联的聚乙烯 (PE) 链的结合能 (BE) 的密度泛函理论 (DFT) 泛函以 DLPNO-CCSD(T) 和 DLPNO-CCSD(T1) 数据为基准。PEX-M-PEX 复合物与普通平行 PEX…相比，X = 3-9 个碳原子的 PEX 链是以共价 CMC 键和链间分散相互作用的协同效应为特征的模型物种。DLPNO-CC 方法的准确性通过将 BE 与小 PE3-M-PE3 复合物的规范 CCSD(T) 结果进行比较来评估。PEX…PEX 和闭壳 PEX-M-PEX 复合物 (M = Be, Mg, Zn) 的功能性以 DLPNO-CCSD(T) BE 为基准；开壳复合物（M = Li、Ag、Au）与具有迭代三元组的 DLPNO-CCSD(T1) 方法进行了基准测试。三个色散校正与 25 个 DFT 函数相结合，用于计算使用 def2-TZVPP 和 def2-QZVPP 基组的 PEX-M 和 PEX 片段的 BE。闭壳 PEX-M-PEX 复合物的精度在 5% 以内是通过五个功能实现的。开壳 PEX-M-PEX 复合物的泛函不太准确；只有两个泛函与 DLPNO-CCSD(T1) 的偏差小于 15%。特别有问题的是 PEX-Li-PEX 复合物。对于范围分离的混合泛函 ωB97X-D3 和 CAM-B3LYP/D3(BJ)-ABC，就平均绝对百分比误差而言，所有复合物的整体性能都合理。闭壳 PEX-M-PEX 复合物的精度在 5% 以内是通过五个功能实现的。开壳 PEX-M-PEX 复合物的泛函不太准确；只有两个泛函与 DLPNO-CCSD(T1) 的偏差小于 15%。特别有问题的是 PEX-Li-PEX 复合物。对于范围分离的混合泛函 ωB97X-D3 和 CAM-B3LYP/D3(BJ)-ABC，就平均绝对百分比误差而言，所有复合物的整体性能都合理。闭壳 PEX-M-PEX 复合物的精度在 5% 以内是通过五个功能实现的。开壳 PEX-M-PEX 复合物的泛函不太准确；只有两个泛函与 DLPNO-CCSD(T1) 的偏差小于 15%。特别有问题的是 PEX-Li-PEX 复合物。对于范围分离的混合泛函 ωB97X-D3 和 CAM-B3LYP/D3(BJ)-ABC，就平均绝对百分比误差而言，所有复合物的整体性能都合理。

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DFT Functionals for Modeling of Polyethylene Chains Cross-Linked by Metal Atoms. DLPNO–CCSD(T) Benchmark Calculations

Density functional theory (DFT) functionals for calculations of binding energies (BEs) of the polyethylene (PE) chains cross-linked by selected metal atoms (M) are benchmarked against DLPNO–CCSD(T) and DLPNO–CCSD(T1) data. PEX-M-PEX complexes as compared with plain parallel PEX···PEX chains with X = 3–9 carbon atoms are model species characterized by a cooperative effect of covalent C-M-C bonds and interchain dispersion interactions. The accuracy of DLPNO–CC methods was assessed by a comparison of BEs with the canonical CCSD(T) results for small PE3-M-PE3 complexes. Functionals for PEX···PEX and closed-shell PEX-M-PEX complexes (M = Be, Mg, Zn) were benchmarked against DLPNO–CCSD(T) BEs; open-shell complexes (M = Li, Ag, Au) were benchmarked against the DLPNO–CCSD(T1) method with iterative triples. Three dispersion corrections were combined with 25 DFT functionals for calculations of BEs with respect to PEX-M and PEX fragments employing def2-TZVPP and def2-QZVPP basis sets. Accuracy to within 5% for the closed-shell PEX-M-PEX complexes was achieved with five functionals. Less accurate are functionals for the open-shell PEX-M-PEX complexes; only two functionals deviate by less than 15% from DLPNO–CCSD(T1). Particularly problematic were PEX-Li-PEX complexes. A reasonable overall performance across all complexes in terms of the mean absolute percentage error is found for the range-separated hybrid functionals ωB97X-D3 and CAM-B3LYP/D3(BJ)-ABC.

更新日期：2021-09-02

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