半经验或非经验的双混合密度泛函：哪个更健壮？<a href="#fn1" title="可用电子补充信息（ESI）：用于DFT-D3色散校正的阻尼参数。色散校正与未校正的结果。加权总平均绝对偏差。所有统计结果及其分析。参见DOI：10.1039 / c8cp03852j">†</a>,Physical Chemistry Chemical Physics

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半经验或非经验的双混合密度泛函：哪个更健壮？†
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2018-07-23 00:00:00 , DOI: 10.1039/c8cp03852j
Nisha Mehta _{1,

2,

3,

4} , Marcos Casanova-Páez _{1,

2,

3,

4} , Lars Goerigk _{1,

2,

3,

4}

Affiliation

非经验性双混合密度泛函（DHDF）的发展是一个非常活跃的研究领域，该领域中的方法数量迅速增加。同时，缺乏发表的工作可以公平地评估和比较非经验性和半经验性的DHDF。在本文中，我们弥合了这一差距，并在大型GMTKN55基准数据库上针对两类DHDF进行了全面分析，以分析一般主族的热化学，动力学和非共价相互作用[Goerigk等。，物理化学化学物理 ，2017年，19，32184–32215]。总共测试了115种经色散校正和未经校正的DHDF，这将有助于对31种方法进行深入评估：19种非经验性DHDF和12种半经验性DHDF。因此，我们的研究代表了有史以来规模最大的DHDF研究，可以作为向方法开发者和用户提供信息的重要基准。我们的结果表明，半经验DHDF是最可靠的密度泛函近似值，比非经验的DHDF更可靠和准确。实际上，某些非经验方法甚至优于混合方法，甚至是色散校正和未经校正的MP2和SCS-MP2。SOS0-PBE0-2-D3（BJ）是我们可以放心推荐的通用性的唯一例外，也是唯一的非经验性DHDF。但是，它仍然胜过六个半经验的DHDF，其中我们特别要推荐以下五种：ωB97X-2-D3（BJ），DSD-BLYP-D3（BJ），DSD-PBEP86-D3（BJ），B2NC-PLYP-D3（BJ）和B2GPPLYP -D3（BJ）。我们的发现严重质疑该领域的当前趋势，并且他们强调必须找到新颖的策略才能胜过目前市场上最好的密度泛函理论方法。我们希望我们的研究可以成为激发这种领域变化方向的重要基石。

"点击查看英文标题和摘要"

Semi-empirical or non-empirical double-hybrid density functionals: which are more robust?†

The development of non-empirical double-hybrid density functionals (DHDFs) is a very active research area with the number of approaches in this field having increased rapidly. At the same time, there is a lack of published work that provides a fair assessment and comparison between non-empirical and semi-empirical DHDFs on an equal footing. Herein, we close this gap and present a thorough analysis of both classes of DHDFs on the large GMTKN55 benchmark database for general main-group thermochemistry, kinetics, and noncovalent interactions [Goerigk et al., Phys. Chem. Chem. Phys., 2017, 19, 32184–32215]. In total, 115 variations of dispersion-corrected and -uncorrected DHDFs are tested, which will be condensed to an in-depth assessment of 31 methods: 19 non-empirical and 12 semi-empirical DHDFs. As such, our study represents the largest DHDF study ever conducted and can serve as an important benchmark informing method developers and users alike. Our results show that semi-empirical DHDFs are the most robust density functional approximations and more reliable and accurate than non-empirical ones. In fact, some non-empirical approaches are even outperformed by hybrid approaches or even dispersion-corrected and -uncorrected MP2 and SCS-MP2. SOS0-PBE0-2-D3(BJ) is the only exception and the only non-empirical DHDF that we can safely recommend for general applicability. However, it is still outperformed by six semi-empirical DHDFs, of which we would like to particularly recommend the following five: ωB97X-2-D3(BJ), DSD-BLYP-D3(BJ), DSD-PBEP86-D3(BJ), B2NC-PLYP-D3(BJ), and B2GPPLYP-D3(BJ). Our findings seriously question current trends in the field and they highlight that novel strategies have to be found in order to outperform the currently best density functional theory methods on the market. We hope that our study can function as an important cornerstone inspiring such a change of direction in the field.

更新日期：2018-07-23

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