Estimates of the ab initio limit for π-π interactions:: The benzene dimer
Estimates of the ab initio limit for π-π interactions:: The benzene dimer
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DOI：
10.1021/ja025896h
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发表时间：
2002-09-11
影响因子：
15
通讯作者：
Sherrill, CD
中科院分区：
文献类型：
--
作者：
Sinnokrot, MO;Valeev, EF;Sherrill, CD
最先进的电子结构方法已经应用于芳香pi-pi相互作用的最简单的原型，苯晚餐。通过与大的aug-cc-pVTZ基集的结果比较，我们证明了aug-cc-pVDZ等较小的基集足以在二阶Moller-Plesset摄动理论（MP2）水平上进行分子间参数的几何优化。然而，比8 -cc- pvtz更大的基集对于精确的结合能很重要。通过显式相关MP2- r12 /A技术估计的完整基集MP2结合能的量级明显大于先前的估计。当通过单、双和摄动三元组[CCSD(T)]的耦合簇对高阶相关效应进行校正时，发现三明治、T形和平行位移构型的结合能d （Do）分别为1.8（2.0）、2.7（2.4）和2.8 (2.7)kcal mol（-1）。
State-of-the-art electronic structure methods have been applied to the simplest prototype of aromatic pi-pi interactions, the benzene dinner. By comparison to results with a large aug-cc-pVTZ basis set, we demonstrate that more modest basis sets such as aug-cc-pVDZ are sufficient for geometry optimizations of intermolecular parameters at the second-order Moller-Plesset perturbation theory (MP2) level. However, basis sets even larger than aug-cc-pVTZ are important for accurate binding energies. The complete basis set MP2 binding energies, estimated by explicitly correlated MP2-R12/A techniques, are significantly larger in magnitude than previous estimates. When corrected for higher-order correlation effects via coupled cluster with singles, doubles, and perturbative triples [CCSD(T)], the binding energies D. (Do) for the sandwich, T-shaped, and parallel-displaced configurations are found to be 1.8 (2.0), 2.7 (2.4), and 2.8 (2.7) kcal mol(-1), respectively.