Matveeva Regina, Falck Erichsen Merete, Koch Henrik, Høyvik Ida-Marie
Department of Chemistry, Norwegian University of Science and Technology (NTNU), Trondheim, Norway.
Scuola Normale Superiore, Pisa, Italy.
J Comput Chem. 2022 Jan 15;43(2):121-131. doi: 10.1002/jcc.26777. Epub 2021 Nov 5.
In this article we use MP2 and CCSD(T) calculations for the A24 and S66 data sets to explore how midbond functions can be used to generate cost effective counterpoise corrected supramolecular interaction energies of noncovalent complexes. We use the A24 data set to show that the primary role of midbond functions is not to approach the complete basis set limit, but rather to ensure a balanced description of the molecules and the interaction region (unrelated to the basis set superposition error). The need for balance is a consequence of using atom centered basis sets. In the complete basis set limit, the error will disappear, but reaching the complete basis set limit is not feasible beyond small systems. For S66 we investigate the need for increasing the number of midbond centers. Results show that adding a second midbond center increases the accuracy, but the effect is secondary to changing the atom centered basis set. Further, by comparing calculations using the 3s3p2d1f1g midbond set with using aug-cc-pVDZ and aug-cc-pVTZ as midbond sets, we see that the requirements for the midbond set to be effective, is not just that it contains diffuse functions, but also that high angular momentum functions are included. By comparing two approaches for placing midbond centers we show that results are not particularly sensitive to placement as long as the placement is reasonable.
在本文中，我们对A24和S66数据集使用MP2和CCSD(T)计算方法，以探究如何利用键中函数来生成具有成本效益的非共价复合物的抵消校正超分子相互作用能。我们使用A24数据集表明，键中函数的主要作用不是接近完全基组极限，而是确保对分子和相互作用区域进行平衡描述（与基组叠加误差无关）。平衡的必要性是使用以原子为中心的基组的结果。在完全基组极限下，误差将消失，但对于小系统之外的情况，达到完全基组极限是不可行的。对于S66，我们研究了增加键中中心数量的必要性。结果表明，添加第二个键中中心可提高准确性，但效果相对于改变以原子为中心的基组来说是次要的。此外，通过比较使用3s3p2d1f1g键中基组与使用aug-cc-pVDZ和aug-cc-pVTZ作为键中基组的计算，我们发现键中基组有效的要求不仅是它包含弥散函数，还包括包含高角动量函数。通过比较放置键中中心的两种方法，我们表明只要放置合理，结果对放置就不是特别敏感。
