Department of Chemistry, University of Michigan, Ann Arbor, MI, 48109, USA.
Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093, Warszawa, Poland.
J Mol Model. 2020 Apr 15;26(5):102. doi: 10.1007/s00894-020-4340-9.
This work examines the suitability of meta-GGA functionals for symmetry-adapted perturbation theory (SAPT) calculations. The assessment is based on the term-by-term comparison with the benchmark SAPT variant based on coupled-cluster singles and doubles description of monomers, SAPT(CCSD). Testing systems include molecular complexes ranging from strong to weak and the He dimer. The following nonempirical meta-GGAs are examined: TPSS, revTPSS, MVS, SCAN, and SCAN0 with and without the asymptotic correction (AC) of the exchange-correlation potential. One range-separated meta-GGA functional, LC-PBETPSS, is also included. The AC-corrected pure meta-GGAs (with the exception of MVS) represent a definite progress in SAPT(DFT) compared to pure GGA, such as PBEAC, with their more consistent predictions of energy components. However, none of the meta-GGAs is better than the hybrid GGA approach SAPT(PBE0AC). The SAPT(DFT) electrostatic energy offers the most sensitive probe of the quality of the underlying DFT density. Both SCAN- and TPSS-based electrostatic energies agree with reference to within 5% or better which is an excellent result. We find that SCAN0 can be used in SAPT without the AC correction. The long-range corrected LC-PBETPSS is a reliable performer both for the components and total interaction energies.
这项工作考察了泛函在对称适应微扰理论（SAPT）计算中的适用性。评估是基于与基于单体耦合簇单双描述的基准 SAPT 变体（SAPT(CCSD)）的逐项比较。测试体系包括从强到弱的分子复合物和氦二聚体。研究了以下非经验泛函：TPSS、revTPSS、MVS、SCAN 和带有和不带有交换相关势渐近校正（AC）的 SCAN0。还包括一种范围分离的泛函 LC-PBETPSS。与纯 GGA（如 PBEAC）相比，修正后的纯泛函（除了 MVS 之外）在 SAPT(DFT)中代表了明显的进步，它们对能量分量的预测更加一致。然而，没有一个泛函比混合 GGA 方法 SAPT(PBE0AC)更好。SAPT(DFT)的静电能提供了对基础密度泛函质量的最敏感的探针。基于 SCAN 和 TPSS 的静电能与参考值的误差在 5%以内，这是一个极好的结果。我们发现，在 SAPT 中可以不使用 AC 校正来使用 SCAN0。长程修正的 LC-PBETPSS 在各分量和总相互作用能方面都是可靠的。
