Department of Physical Chemistry, University of Santiago de Compostela, Avda. Alfonso X El Sabio s/n, Lugo, 27001, Spain.
Department of Physical Chemistry, University of Santiago de Compostela, Avda. das Ciencias s/n, Santiago de Compostela, 15782, Spain.
J Comput Chem. 2018 Jan 15;39(2):93-104. doi: 10.1002/jcc.25084. Epub 2017 Oct 26.
The characteristics of the concave-convex π-π interactions are evaluated in 32 buckybowl dimers formed by corannulene, sumanene, and two substituted sumanenes (with S and CO groups), using symmetry-adapted perturbation theory [SAPT(DFT)] and density functional theory (DFT). According to our results, the main stabilizing contribution is dispersion, followed by electrostatics. Regarding the ability of DFT methods to reproduce the results obtained with the most expensive and rigorous methods, TPSS-D seems to be the best option overall, although its results slightly tend to underestimate the interaction energies and to overestimate the equilibrium distances. The other two tested DFT-D methods, B97-D2 and B3LYP-D, supply rather reasonable results as well. M06-2X, although it is a good option from a geometrical point of view, leads to too weak interactions, with differences with respect to the reference values amounting to about 4 kcal/mol (25% of the total interaction energy). © 2017 Wiley Periodicals, Inc.
采用对称自适应微扰理论（SAPT(DFT)）和密度泛函理论（DFT），评估了由蔻烯、 sumanene 和两种取代的 sumanene（具有 S 和 CO 基团）组成的 32 个 buckybowl 二聚体中凹凸 π-π 相互作用的特性。根据我们的结果，主要的稳定贡献是色散，其次是静电。关于 DFT 方法再现最昂贵和最严格方法获得的结果的能力，TPSS-D 总体上似乎是最佳选择，尽管其结果略微倾向于低估相互作用能并高估平衡距离。另外两种测试的 DFT-D 方法，B97-D2 和 B3LYP-D，也提供了相当合理的结果。M06-2X 虽然从几何角度来看是一个不错的选择，但会导致相互作用太弱，与参考值的差异约为 4 kcal/mol（总相互作用能的 25%）。©2017 Wiley Periodicals, Inc.
