Kozuch Sebastian, Bachrach Steven M, Martin Jan M L
Department of Chemistry and Center for Advanced Scientific Computing and Modeling (CASCaM), University of North Texas , Denton, Texas 76201, United States.
J Phys Chem A. 2014 Jan 9;118(1):293-303. doi: 10.1021/jp410723v. Epub 2013 Dec 20.
Explicitly correlated CCSD(T) valence basis limit relative energies were obtained for the 65 conformers of butane-1,4-diol, a prototypical system with a strong internal hydrogen bond. The performance of a variety of ab initio and DFT methods (with and without empirical dispersion corrections) was assessed in detail. Consideration of all pairwise conformer energies provides a performance gauge for both H-bonds and van der Waals interactions, aside from internal strain of angles and bonds. In the post-HF realm, it was found that SCS(MI)CCSD-F12/cc-pVDZ-F12 can be a cost-effective alternative to CCSD(T)/CBS, almost without any loss in accuracy. In the DFT arena, the double-hybrid DSD-PBEP86-D3BJ surpasses the accuracy of all other methods (except for SCS(MI)CCSD, but at a small fraction of its cost). Several hybrid functionals provide an acceptable accuracy with the def2-QZVP basis set, especially BMK, M06, LC-ωPBE-D3, and TPSS0-D3. With the more modest 6-311+G(d,p) basis set, the H-bonds are far from basis set completeness and, due to error compensation, the inclusion of a dispersion correction is generally counterproductive. Some functionals that represent "Pauling points" at this level are LC-ωPBE, TPSS0, B1B95, BMK, TPSSh, PBE0, TPSS, and ωB97X.
获得了丁二醇-1,4-二醇65种构象异构体的显式相关耦合簇单双激发三重微扰（CCSD(T)）价基极限相对能量，丁二醇-1,4-二醇是具有强分子内氢键的典型体系。详细评估了各种从头算和密度泛函理论（DFT）方法（有无经验色散校正）的性能。除了角度和键的内应变外，考虑所有成对构象异构体能量为氢键和范德华相互作用提供了一个性能指标。在后哈特里-福克（HF）领域，发现二阶微扰修正的二次组态相互作用（SCS(MI)CCSD）-F12/cc-pVDZ-F12几乎在不损失任何精度的情况下，是CCSD(T)/完全基组（CBS）具有成本效益的替代方法。在DFT领域，双杂化泛函DSD-PBEP86-D3BJ的精度超过了所有其他方法（除了SCS(MI)CCSD，但成本仅为其一小部分）。几种杂化泛函在def2-QZVP基组下提供了可接受的精度，特别是BMK、M06、LC-ωPBE-D3和TPSS0-D3。使用更适度的6-311+G(d,p)基组时，氢键远未达到基组完备性，并且由于误差补偿，包含色散校正通常会适得其反。在此水平上代表“鲍林点”的一些泛函有LC-ωPBE、TPSS0、B1B95、BMK、TPSSh、PBE0、TPSS和ωB97X。
