Santra Golokesh, Semidalas Emmanouil, Martin Jan M L
Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, 7610001 Reḥovot, Israel.
J Phys Chem Lett. 2021 Sep 30;12(38):9368-9376. doi: 10.1021/acs.jpclett.1c02838. Epub 2021 Sep 22.
By adding a GLPT3 (third-order Görling-Levy perturbation theory, or KS-MP3) term to the XYG7 form for a double hybrid, we are able to bring down WTMAD2 (weighted total mean absolute deviation) for the very large and chemically diverse GMTKN55 benchmark to an unprecedented 1.17 kcal/mol, competitive with much costlier composite wave function ab initio approaches. Intriguingly, (a) the introduction of makes an empirical dispersion correction redundant; (b) generalized gradient approximation (GGA) or meta-GGA semilocal correlation functionals offer no advantage over the local density approximation (LDA) in this framework; (c) if a dispersion correction is retained, then simple Slater exchange leads to no significant loss in accuracy. It is possible to create a six-parameter functional with WTMAD2 = 1.42 that has no post-LDA density functional theory components and no dispersion correction in the final energy.
通过在双杂化的XYG7形式中添加一个GLPT3（三阶戈林-利维微扰理论，即KS-MP3）项，我们能够将非常大且化学性质多样的GMTKN55基准的WTMAD2（加权总平均绝对偏差）降至前所未有的1.17 kcal/mol，与成本高得多的复合波函数从头算方法具有竞争力。有趣的是，（a）该引入使得经验色散校正变得多余；（b）在这个框架中，广义梯度近似（GGA）或元GGA半局部相关泛函相对于局部密度近似（LDA）没有优势；（c）如果保留色散校正，那么简单的斯莱特交换不会导致精度有显著损失。有可能创建一个WTMAD2 = 1.42的六参数泛函，该泛函在最终能量中没有后LDA密度泛函理论成分且没有色散校正。
