Institut für Theoretische Chemie , Universität Stuttgart , Pfaffenwaldring 55 , D-70569 Stuttgart , Germany.
J Chem Theory Comput. 2019 Feb 12;15(2):1044-1052. doi: 10.1021/acs.jctc.8b01098. Epub 2019 Jan 28.
We present benchmark results for the A24, S66, and X40 sets of intermolecular interaction energies obtained with our recently developed PNO-LCCSD(T)-F12 method. Using the aug-cc-pVQZ-F12 basis set and tight domain options, the root-mean-square (RMSD) and maximum (MAXD) deviations from the currently best CCSD(T)/CBS estimates for the S66 set amount to only 0.02 and 0.06 kcal mol, respectively. The corresponding triple-ζ (aug-cc-pVTZ-F12) results are similarly accurate, and even with double-ζ (aug-cc-pVDZ-F12) basis sets the RMSD and MAXD deviations amount to only 0.05 and 0.11 kcal mol, respectively. Preliminary PNO-LCCSD(T)-F12 calculations on the X40 set of intermolecular interactions of halogenated molecules yield interaction energies in reasonable agreement with the original CCSD(T)/CBS estimates. The PNO-LCCSD(T)-F12 method does not rely on error cancellations as the popular ΔCCSD(T) approach and can yield comparable or better accuracy at a fraction of the cost. This accuracy is of importance for studying reactions involving large molecules, in which intramolecular noncovalent interactions are important and no counterpoise corrections are possible.
我们呈现了使用最近开发的 PNO-LCCSD(T)-F12 方法获得的 A24、S66 和 X40 组分子间相互作用能的基准测试结果。使用 aug-cc-pVQZ-F12 基组和紧密域选项，S66 组的均方根（RMSD）和最大（MAXD）偏差与当前最好的 CCSD(T)/CBS 估计值仅分别为 0.02 和 0.06 kcal/mol。相应的三重ζ（aug-cc-pVTZ-F12）结果同样准确，即使使用双ζ（aug-cc-pVDZ-F12）基组，RMSD 和 MAXD 偏差也仅分别为 0.05 和 0.11 kcal/mol。对卤代分子的 X40 组分子间相互作用的初步 PNO-LCCSD(T)-F12 计算得出的相互作用能与原始 CCSD(T)/CBS 估计值相当吻合。PNO-LCCSD(T)-F12 方法不依赖于流行的ΔCCSD(T)方法的误差抵消，并且可以以成本的一小部分获得可比或更好的精度。对于研究涉及大分子的反应，这种精度非常重要，因为在这些反应中，分子内非共价相互作用很重要，并且不可能进行对消校正。
