过渡金属配合物与大π共轭体系的结合能。密度泛函理论与后Hartree-Fock方法的比较。,The Journal of Physical Chemistry A

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过渡金属配合物与大π共轭体系的结合能。密度泛函理论与后Hartree-Fock方法的比较。
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2007 Aug 2 , DOI: 10.1021/jp0708648
Atsushi Ikeda ₁ , Yoshihide Nakao ₁ , Hirofumi Sato ₁ , Shigeyoshi Sakaki ₁

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我们系统地评估了d10，d8和d6过渡金属配合物与各种pi共轭体系（例如Pt（PH3）2 {C2H4-n（CH = CH2）n}，Pd（PH3）2 {C2H4- n（CH = CH2）n}，[PtCl3 {C2H4-n-（CH = CH2）n}]-，[PdCl3 {C2H4-n（CH = CH2）n}]-和[PtCl5 {C2H4-n（ CH = CH2）n}]-（n = 0-4），使用MP2至MP4，CCSD（T）和密度泛函理论（DFT）方法。MP4（SDQ）和CCSD（T）方法具有可靠的结合能，而当pi共轭体系的尺寸较大时，DFT方法会大大低估结合能。低估的发生与坐标键的性质无关；如预期的那样，pi-back捐赠比pt-（0）配合物中的σ-捐赠更强，在pt（II）复合物中与pi-back捐赠具有可比性，并且只有σ-捐赠参与了Pt（0）的配位键（ IV）配合物。DFT方法提供比MP4（SDQ）方法适度更强的电荷转移（CT）相互作用，这表明DFT方法对结合能的低估并不是由于CT相互作用的描述不足而引起的。从几个模型系统的理论研究得出结论，低估是由于对电子相关效应的描述不足而引起的。

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Binding energy of transition-metal complexes with large pi-conjugate systems. Density functional theory vs post-Hartree-Fock methods.

We systematically evaluated the binding energies of d10, d8, and d6 transition-metal complexes with various pi-conjugate systems such as Pt(PH3)2{C2H4-n(CH=CH2)n}, Pd(PH3)2{C2H4-n(CH=CH2)n}, [PtCl3{C2H4-n-(CH=CH2)n}]-, [PdCl3{C2H4-n(CH=CH2)n}]-, and [PtCl5{C2H4-n(CH=CH2)n}]- (n = 0-4) using the MP2 to MP4, CCSD(T), and density functional theory (DFT) methods. The MP4(SDQ) and CCSD(T) methods present a reliable binding energy, whereas the DFT method significantly underestimates the binding energy when the size of the pi-conjugate system is large. The underestimation occurs independently of the coordinate bonding nature; the pi-back-donation is stronger than the sigma-donation in the Pt(0) complexes, as expected, they are comparable in the Pt(II) complexes, and only the sigma-donation participates in the coordinate bond of the Pt(IV) complexes. The DFT method provides moderately stronger charge-transfer (CT) interaction than the MP4(SDQ) method, suggesting that the underestimation of the binding energy by the DFT method does not arise from the insufficient description of the CT interaction. From theoretical investigation of several model systems, it is concluded that the underestimation arises from the insufficient description of electron correlation effects.

更新日期：2017-01-31

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