Calculation of Heats of Formation for Zn Complexes: Comparison of Density Functional Theory, Second Order Perturbation Theory, Coupled-Cluster and Complete Active Space Methods.
Calculation of Heats of Formation for Zn Complexes: Comparison of Density Functional Theory, Second Order Perturbation Theory, Coupled-Cluster and Complete Active Space Methods.
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DOI：
10.1021/ct400856g
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发表时间：
2013-12-10
影响因子：
5.5
通讯作者：
Gagliardi, Laura
中科院分区：
文献类型：
--
作者：
Weaver, Michael N.;Merz, Kenneth M., Jr.;Ma, Dongxia;Kim, Hyun Jung;Gagliardi, Laura
使用十四种密度泛函、MP2 计算以及 CCSD 和 CCSD(T) 耦合簇方法预测了 9 种 ZnX 配合物（X= Zn、H、O、F2、S、Cl、Cl2、CH3、(CH3)2）的形成热。计算利用相关一致的 cc-pVTZ 和 aug-cc-pVTZ 基组。 TPSSTPSS 和 TPSSKCIS 密度泛函对生成热的预测最为准确，而 BLYP、B3LYP、MP2、CCSD 和 CCSD(T) 水平是基于准确度表现最差的方法之一。预测了大范围的 Zn2 平衡键距，表明许多研究水平的理论可能无法充分描述这种过渡金属二聚体。为了进一步衡量密度泛函方法的准确性，进行了高级 CASSCF 和 CASPT2 计算，以估计双原子 Zn 配合物的键解离能、平衡键长和形成热，并将后两个量与 DFT、MP2 和耦合团簇计算的结果以及实验值进行比较。
Heats of formation were predicted for nine ZnX complexes (X= Zn, H, O, F2, S, Cl, Cl2, CH3, (CH3)2) using fourteen density functionals, MP2 calculations and the CCSD and CCSD(T) coupled-cluster methods. Calculations utilized the correlation consistent cc-pVTZ and aug-cc-pVTZ basis sets. Heats of formation were most accurately predicted by the TPSSTPSS and TPSSKCIS density functionals, and the BLYP, B3LYP, MP2, CCSD and CCSD(T) levels were among the poorest performing methods based on accuracy. A wide range of Zn2 equilibrium bond distances were predicted, indicating that many of the studied levels of theory may be unable to adequately describe this transition metal dimer. To further benchmark the accuracy of the density functional methods, high-level CASSCF and CASPT2 calculations were performed to estimate bond dissociation energies, equilibrium bond lengths and heats of formation for the diatomic Zn complexes and the latter two quantities were compared with the results of DFT, MP2 and coupled-cluster calculations as well as experimental values.
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