Density fitting and Cholesky decomposition approximations in symmetry-adapted perturbation theory: Implementation and application to probe the nature of π-π interactions in linear acenes
Density fitting and Cholesky decomposition approximations in symmetry-adapted perturbation theory: Implementation and application to probe the nature of π-π interactions in linear acenes
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DOI：
10.1063/1.3426316
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发表时间：
2010-05-14
影响因子：
4.4
通讯作者：
Sherrill, C. David
中科院分区：
文献类型：
--
作者：
Hohenstein, Edward G.;Sherrill, C. David
密度拟合（DF）近似已经被用于提高几种量子力学方法的效率。在这项工作中，我们应用DF和相关的方法，Cholesky分解（CD），波函数为基础的自适应微扰理论（SAPT）。我们还测试了Cholesky分解的单中心近似。DF和CD近似导致SAPT的整体计算成本的显着改善，同时引入可以忽略不计的误差。对于典型的目标精度，所需的Cholesky基明显小于DF基（尽管构造Cholesky向量的成本略大于构造三指标DF积分的成本）。在这项工作中开发的SAPT程序应用于并苯之间的相互作用以前研究的格里姆[Angew。化学成分：Int.Ed.47，3430（2008）]，通过加入并五苯二聚体扩展了研究的情况。SAPT分解的并苯相互作用提供了一个更现实的图片的相互作用比以前报道的能量分解分析。这些数据表明，平行位移和T形并苯二聚体都具有特殊的稳定π-π相互作用所产生的电子相关项，这是显着更稳定的基础上成对C6 R-6估计比预期的。这些术语在T形几何中与平行位移几何中定性相同，尽管它们在T形几何中大约小2倍，因为分子间电子对之间的距离更大。(C)2010年美国物理学会。[doi：10.1063/1.3426316]
Density fitting (DF) approximations have been used to increase the efficiency of several quantum mechanical methods. In this work, we apply DF and a related approach, Cholesky decomposition (CD), to wave function-based symmetry-adapted perturbation theory (SAPT). We also test the one-center approximation to the Cholesky decomposition. The DF and CD approximations lead to a dramatic improvement in the overall computational cost of SAPT, while introducing negligible errors. For typical target accuracies, the Cholesky basis needed is noticeably smaller than the DF basis (although the cost of constructing the Cholesky vectors is slightly greater than that of constructing the three-index DF integrals). The SAPT program developed in this work is applied to the interactions between acenes previously studied by Grimme [Angew. Chem., Int. Ed. 47, 3430 (2008)], expanding the cases studied by adding the pentacene dimer. The SAPT decomposition of the acene interactions provides a more realistic picture of the interactions than that from the energy decomposition analysis previously reported. The data suggest that parallel-displaced and T-shaped acene dimers both feature a special stabilizing pi-pi interaction arising from electron correlation terms which are significantly more stabilizing than expected on the basis of pairwise -C6R-6 estimates. These terms are qualitatively the same in T-shaped as in parallel-displaced geometries, although they are roughly a factor of 2 smaller in T-shaped geometries because of the larger distances between the intermolecular pairs of electrons. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3426316]