A density-functional study on π-aromatic interaction:: Benzene dimer and naphthalene dimer -: art. no. 104307
A density-functional study on π-aromatic interaction:: Benzene dimer and naphthalene dimer -: art. no. 104307
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DOI：
10.1063/1.2011396
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发表时间：
2005-09-08
影响因子：
4.4
通讯作者：
Hirao, K
中科院分区：
文献类型：
--
作者：
Sato, T;Tsuneda, T;Hirao, K
应用密度泛函理论（DFT）的远程校正（LC）方案计算了苯二聚体和萘二聚体的-芳香相互作用。在之前的计算中，LC方案被证实[Iikura， J. Chem.]通过结合Anderson-Langreth-Lundqvist (ALL) vdW相关泛函，给出了非常精确的小范德华（vdW）配合物的势能面（PESs） [Andersson, Phys。]生物工程学报，2003,14(1):1 - 2。在这项研究中，LC-DFT+ALL方法通过计算苯二聚体的大范围PES，包括平行、t形和平行位移构型来检验。结果表明，在PES的所有参考点上，我们成功地在小于1 kcal/mol的能量偏差范围内再现了非常精确的PES，与高水平从头算分子轨道方法的结果相比。还发现LC-DFT+ALL给出了独立于所使用的交换相关泛函的准确结果，与传统纯泛函的强函数依赖性形成鲜明对比。这表明，交换排斥和范德华吸引相互作用都应该正确地纳入传统的纯泛函，以便计算准确的-芳香相互作用。我们还发现LC-DFT+ALL方法在计算芳香相互作用时具有较低的基集依赖性。该方案也成功地应用于pi，…，萘二聚体的堆叠相互作用。这可能表明LC-DFT+ALL方法将成为计算生物分子等大分子的有力工具。(c) 2005年美国物理研究所。
The long-range correction (LC) scheme of density-functional theory (DFT) was applied to the calculation of the pi-aromatic interaction of the benzene dimer and naphthalene dimer. In previous calculations, it was confirmed that the LC scheme [Iikura , J. Chem. Phys. 115, 3540 (2001)] gives very accurate potential-energy surfaces (PESs) of small van der Waals (vdW) complexes by combining with the Anderson-Langreth-Lundqvist (ALL) vdW correlation functional [Andersson , Phys. Rev. Lett. 76, 102 (1996)] (LC-DFT+ALL). In this study, LC-DFT+ALL method was examined by calculating a wide range of PES of the benzene dimer including parallel, T-shaped, and parallel-displaced configurations. As a result, we succeeded in reproducing very accurate PES within the energy deviance of less than 1 kcal/mol in comparison with the results of high-level ab initio molecular-orbital methods at all reference points on the PES. It was also found that LC-DFT+ALL gave accurate results independent of exchange-correlation functional used, in contrast with the strong functional dependencies of conventional pure functionals. This indicates that both exchange repulsion and van der Waals attractive interactions should be correctly incorporated in conventional pure functionals in order to calculate accurate pi-aromatic interactions. We also found that LC-DFT+ALL method has a low basis-set dependency in the calculations of pi-aromatic interactions. The present scheme was also successfully applied to the pi,...,pi stacking interactions of naphthalene dimer. This may suggest that LC-DFT+ALL method would be a powerful tool in the calculations of large molecules such as biomolecules. (c) 2005 American Institute of Physics.