Importance of van der Waals Descriptions on Accurate Isomerization Energy Calculations of Thiourea Compounds: LCgau-BOP+LRD Method,The Journal of Physical Chemistry A

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Importance of van der Waals Descriptions on Accurate Isomerization Energy Calculations of Thiourea Compounds: LCgau-BOP+LRD Method
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2019-07-19 00:00:00 , DOI: 10.1021/acs.jpca.9b04149
Dae-Hwan Ahn ₁ , Takeshi Sato ₂ , Jong-Won Song _{1,

3} , Kimihiko Hirao _{3,

4}

Affiliation

We have previously reported that, whereas conventional density functional theory (DFT) functionals have provided poor calculations on the alkane isodesmic reaction energy and isomerization reaction energy of organic molecules that include C, N, and O atoms, our developed long-range corrected (LC)- and LC including Gaussian attenuation (LCgau)-DFT + local response dispersion (LRD) functionals, which can accurately calculate inter- and intramolecular weak interactions, give accurate isomerization energies on these reactions. In this work, we found that B3LYP-D3, LC-ωPBE-D3, and ωB97XD, known for their good descriptions of weak interaction calculations, fail to reproduce the isomerization reaction energies of the molecules that include the S atom, such as methyl-thiourea, ethyl-thiourea, and propyl-thiourea. In contrast, LC- and LCgau-BOP+LRD functionals provide isomerization reaction energies that are very close to those produced by highly accurate wave function methods. These results show that an accurate description of the intramolecular weak interaction between the alkyl group and the S atom, unlike in the case of urea, is significant to reproduce the correct energy of the molecules with an alkyl group and S atom.

中文翻译：

范德华的重要性关于硫脲化合物精确异构化能量计算的描述：LCgau-BOP + LRD方法

我们先前曾报道过，尽管常规密度泛函理论（DFT）泛函对于包括C，N和O原子的有机分子的烷烃等电势能和异构化反应能的计算结果不佳，但我们开发的远程校正（LC ）和LC（包括高斯衰减（LCgau）-DFT +局部响应分散（LRD）功能），可以准确计算分子间和分子内的弱相互作用，从而在这些反应上提供准确的异构化能。在这项工作中，我们发现以对弱相互作用的良好描述而闻名的B3LYP-D3，LC-ωPBE-D3和ωB97XD无法重现包含S原子的分子（例如甲基-硫脲，乙基硫脲和丙基硫脲。相比之下，LC-和LCgau-BOP + LRD官能团提供的异构化反应能量非常接近于高精度波函数方法产生的能量。这些结果表明，与尿素的情况不同，准确描述烷基和S原子之间的分子内弱相互作用对于再现具有烷基和S原子的分子的正确能量是重要的。

更新日期：2019-07-19

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