The Nonlocal Kernel in van der Waals Density Functionals as an Additive Correction: An Extensive Analysis with Special Emphasis on the B97M-V and ωB97M-V Approaches,Journal of Chemical Theory and Computation

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The Nonlocal Kernel in van der Waals Density Functionals as an Additive Correction: An Extensive Analysis with Special Emphasis on the B97M-V and ωB97M-V Approaches
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2018-10-09 00:00:00 , DOI: 10.1021/acs.jctc.8b00842
Asim Najibi ₁ , Lars Goerigk ₁

Affiliation

The development of van der Waals density functional approximations (vdW-DFAs) has gained considerable interest over the past decade. While in a strictest sense, energy calculations with vdW-DFAs should be carried out fully self-consistently, we demonstrate conclusively for a total of 11 methods that such a strategy only increases the computational time effort without having any significant effect on energetic properties, electron densities, or orbital-energy differences. The strategy to apply a nonlocal vdW-DFA kernel as an additive correction to a fully converged conventional DFA result is therefore justified and more efficient. As part of our study, we utilize the extensive GMTKN55 database for general main-group thermochemistry, kinetics, and noncovalent interactions [Phys. Chem. Chem. Phys.2017, 19, 32184], which allows us to analyze the very promising B97M-V [J. Chem. Phys.2015, 142, 074111] and ωB97M-V [J. Chem. Phys.2016, 144, 214110] DFAs. We also present new DFT-D3(BJ) based counterparts of these two methods and of ωB97X-V [J. Chem. Theory Comput2013, 9, 263], which are faster variants with similar accuracy. Our study concludes with updated recommendations for the general method user, based on our current overview of 325 dispersion-corrected and -uncorrected DFA variants analyzed for GMTKN55. vdW-DFAs are the best representatives of the three highest rungs of Jacob’s Ladder, namely, B97M-V, ωB97M-V, and DSD-PBEP86-NL.

中文翻译：

Van der Waals密度泛函的非局部核作为可加修正：对B97M-V和ωB97M-V方法的特别强调的广泛分析

在过去十年中，范德华密度泛函近似（vdW-DFA）的开发引起了人们的极大兴趣。虽然从最严格的意义上讲，应该完全自洽地使用vdW-DFA进行能量计算，但我们最终证明了总共11种方法，这种策略仅增加了计算时间，而对能量性质，电子没有任何重大影响密度或轨道能量差异。因此，应用非本地vdW-DFA内核作为对完全收敛的常规DFA结果进行加法校正的策略是合理且高效的。作为我们研究的一部分，我们利用广泛的GMTKN55数据库进行一般主族热化学，动力学和非共价相互作用的研究。化学化学物理 2017年，19，32184]，这使我们能够分析非常有前途的B97M-V [ J.化学式物理 2015年，142，074111]和ωB97M-V [ J.化学式物理 2016，144，214110]的DFA。我们还介绍了这两种方法和ωB97X-V的基于DFT-D3（BJ）的新型对应物[ J. Chem。理论COMPUT 2013，9，263]，它们是速度更快的变体，具有相似的准确性。基于对GMTKN55分析的325个色散校正和非校正DFA变体的当前概述，我们的研究在结束时为通用方法用户提供了更新的建议。vdW-DFA是Jacob阶梯的三个最高梯级的最佳代表，分别是B97M-V，ωB97M-V和DSD-PBEP86-NL。

更新日期：2018-10-09

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